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.     

超临界流体辅助醋酸纤维素溶液加工的流变性能

为了改善二醋酸纤维素(CDA)加工的流变性能,采用超临界二氧化碳辅助CDA溶液单螺杆挤出加工,通过狭缝流变仪进行流变测试,研究了注入超临界二氧化碳和加工条件(挤出温度、溶剂含量)对CDA溶液流变行为的影响。结果表明,CDA溶液和CDA/CO_2溶液体系均是非牛顿假塑性流体;CDA溶液和CDA/CO_2溶液体系的剪切黏度随着挤出温度或溶剂量的增加而降低;注入超临界二氧化碳显著降低了CDA溶液的黏度、挤出温度、剪切黏度对温度的敏感程度、口模压力和溶剂量,提高CDA溶液的挤出流量和非牛顿指数。随着温度升高,6 r/min和8 r/min时CDA/CO_2溶液体系黏度下降值大,黏度降低值可以达到47.93%;同一溶剂含量下,6 r/min时注入超临界二氧化碳后CDA溶液黏度下降值较大,降低值可以达到48.10%。     

轮胎胶应力诱导脱硫及对聚丙烯的增韧作用

在轮胎胶粉的熔融挤出过程中添加线型高分子材料作为溶胀剂和承载流体,并通过提高双螺杆挤出机转速的高剪切应力诱导方法,研究了螺杆转速和挤出反应温度对轮胎胶脱硫共混物凝胶含量、熔体流动速率、溶胶特性黏数及红外光谱(FT-IR)的影响。结果表明,双螺杆挤出机的高剪切应力可诱发轮胎胶颗粒中交联网络的断链反应和氧化降解作用,引起脱硫共混物凝胶含量的明显下降、熔体流动速率的明显增加、溶胶特性黏数的明显减小及溶胶分子链中碳碳双键和醚键基团明显增加。在最佳脱硫反应条件下,所得脱硫共混物可使聚丙烯(PP)(J430)材料的缺口冲击强度由10.5kJ/m2提高至47.7kJ/m2。     

三螺杆挤出机挤出特性的数值模拟

利用计算流体力学的方法对聚合物熔体在三螺杆挤出机中的流动规律进行了数值模拟,分析了物料在三螺杆中心区的流动和混合情况。通过速度和压力分布,计算了三螺杆挤出机的螺杆挤出特性参数,并和双螺杆挤出机进行对比分析。结果表明,由于中心区环流的存在,延长了物料在三螺杆挤出机的停留时间分布。三螺杆挤出机在分布性混合、分散性混合、能耗等方面均好于双螺杆挤出机,而产能比又为双螺杆挤出机的1.3倍。三螺杆挤出机具有较好的工程应用前景。     

PVC/稻壳粉复合材料的挤出流变特性

通过甲基丙烯酸甲酯(MMA)在微波作用下改性稻壳粉研究了聚氯乙烯(PVC)/稻壳粉复合材料的流变特性。结果表明,PVC/稻壳粉复合材料为非牛顿性流体,增加稻壳粉的质量份及适当提高熔体温度能减小挤出胀大率。随着剪切速率的增加,挤出物畸变的平均波长和深度均有增加。当剪切速率为230s-1时,挤出物表面光滑;剪切速率为324s-1时,挤出物表面有轻微的鲨鱼皮出现,有轻微的波纹状的畸变,呈蜂窝状;当剪切速率达到523s-1时,有明显的规律性鲨鱼皮畸变,波状物平均波长和平均深度分别达到90μm与20μm。提高温度、增加润滑剂及适当降低挤出速率可降低挤出物畸变的平均波长和深度。     

Application of a response surface method to the optimal design of the wall temperature profiles in extrusion die

A new approach to the optimal design of the die wall temperature profile in polymer extrusion processes is presented. In this approach, optimization of the design variables is conducted by a Response Surface Method (RSM) and the Sequential Quadratic Programming (SQP) algorithm. Design of experiment (DoE) needed for the construction of the response surface is used to evaluate the objective and the constraint functions on the basis of a finite element method (FEM). Two designs of experiments are used and the performances of the optimization results are compared with respect to efficiency and ability to obtain a global optimum. Typically, for extrusion die design, the objective function states that the average velocity across the die exit is uniform. Constraints are used to limit the pressure drop in the die. For this purpose, we optimize the wall temperature profile of a coat hanger die in a heterogeneous way, (i.e. the wall temperature may not be constant in the entire die). The melt temperature enables us to locally control the viscosity, which influences the flows in the various zones. The effect of the design variables in the objective and constraint functions is investigated using Taguchi method. The flow analysis results are then combined with an automatic optimization algorithm to provide a new profile of the die wall temperature distributions.     

Study on the morphology,rheology and surface of dynamically vulcanized chlorinated butyl rubber/polyethylacrylate extrudates: effect of extrusion temperature and times

A high-damping thermoplastic vulcanizate (TPV) composed of chlorinated butyl rubber (CIIR) and polyethylacrylate (PEA) was prepared by using a twin-screw extruder. The effect of extrusion temperature and times on the morphology, rheology and surface of the extrudates was examined and attempts were made to correlate the extrudate surface with the evolution of two-phase morphology and the rheological behavior. CIIR gel content of each extrudate was also analyzed. The result shows that CIIR gel content increases with increasing extrusion temperature or times; furthermore, extrusion at high temperature can produce numerous PEA and CIIR macromolecular radicals, thus chemical links take place between PEA and CIIR molecules. Morphological analysis indicates that phase inversion occurs at a gel content of around 68%, and with increasing extrusion times at high temperature the dispersed particles become larger and the particle edges become blurrier. All CIIR/PEA extrudates show pseudoplastic flow behavior. The extrusion temperature or extrusion times have a significant effect on melt viscosity of the extrudates. Surface analysis exhibits that co-continuous nature of the two-phase morphology results in melt fracture and periodic distortions on the extrudate surface, but with the increasing extrusion temperature or times the surfaces of the extrudates become gradually smooth.     

超声辐照作用下PP/POE共混体系结构与性能的研究

研究了超声辐照对PP/POE共混体系的挤出加工流变行为、力学性能及结晶行为的影响。结果表明:在超声辐照作用下PP/POE共混体系的熔体表观黏度随超声功率的增加而减小,超声辐照能降低口模压力,提高挤出物产量。适宜功率的超声辐照有助于POE粒子的破碎和在PP基体中的均匀分散,改善二者相容性,提高了共混体系的冲击性能。     

Pressure-driven mold filling model of aluminum alloy melt/semi-solid slurry based on rheological behavior

The pressure-driven mold filling ability of aluminum alloy melt/semi-solid slurry is of great significance in pressure casting processes, and the rheological behavior of the alloy has a crucial effect on the mold filling ability according to fluid dynamics. In this work, a pressure-driven mold filling model is first proposed based on the rheological behavior of the alloys. A356 alloy is employed as an example to clarify the rheological behavior of aluminum alloys, which obeys the power law model and is affected by temperature. The rheological behavior of the alloy in semi-solid state is modelled with the coupling of shear rate and temperature. The stop of mold filling attributes to the pressure loss which is caused by the viscosity during the flow of the melt/semi-solid slurry. Pressure loss caused by viscous flow and heat transfer between the alloy and the mold are calculated and coupled during the mold filling of the melt/semi-solid slurry. A pressure-driven mold filling model of aluminum alloy melt/semi-solid slurry is established based on steady-state rheological behavior. The model successfully predicts the filling length of melt/semi-solid slurry in pressure casting processes. Compared with the experimental results,the model can provide a quantitative approach to characterize the pressure-driven mold filling ability of aluminum alloy melt. The model is capable of describing the stop filling behavior of other aluminum alloys in pressure casting processes with corresponding rheological parameters and heat transfer coefficient.     

磷酸酯类偶联剂对CaCO3／HDPE体系偶联效果的研究

研究了自制磷酸酯“W-893”偶联剂对轻质CaCO_3/HDPE的偶联效果。就力学性能(抗张强度、弯曲强度、冲击强度),流变学特性(流动曲线、表现粘度、剪切敏感性、温度敏感性、挤出胀大、压力振荡、熔体破坏)和比重测定的结果发现:“W-893”/CaCO_3/HDPE体系的冲击强度可以为HDPE(5000S)的2～3倍(325目),甚至3～4倍(1250目);弯曲强度提高33.3％,抗张强度下降2.5％,比铝酸酯、钛酸酯的偶联效果好。     

三基发射药单螺杆压伸模具流场仿真及实验验证

为了实现三基发射药生产工艺中的连续化压伸,同时避免模具内部螺旋状流道造成的三基发射药成型的质量和安全问题,应用ANSYS软件模拟了发射药物料在模具内的挤压过程及模针的受力情况。分析了收缩角、出料方向和模具结构对物料在模具中的温度、模具壁面压力、模针表面受力和物料出料速度分布的影响规律,并通过实验进行了验证。结果表明:模具收缩角越大,模具内压力越大,物料温度也越高,且越容易形成热点,同时模针外表面受到的挤压力和摩擦力也越大,模针越容易出现变形和断裂;竖直挤出过程中,模具壁面压力及模针受力均远大于水平挤出中的相应参数,且容易造成挤出后物料的弯曲;增加多孔板有利于物料在挤出模具中的整流和取向,大幅减少物料的径向流动,降低模针在挤出过程中的受力,且成型质量更好。     

单螺杆橡胶挤出机三维非等温流动数值模拟

为研究胶料在挤出过程中的流动模式,本文建立了具有复杂几何构型的主、副螺纹单螺杆螺槽内胶料三维非等温流动的有限元模型,采用Bird-Carreau模型和Arrhenius shear stress方程分别表征胶料黏度随剪切速率和温度的变化,并通过热力学估算确定了合理的机筒壁热学边界条件.在此基础上求解了20 r/min转速下的速度场、温度场和压力场,并将温度数值计算结果与实测结果进行了对比,两者吻合较好,这表明了模型的有效性.此外,通过模拟发现主、副螺纹构型的热喂料螺杆确实可以避免挤出过程中的"死区"并提供更强剪切作用;螺杆挤出段的副螺纹阻碍了胶料的流动,使得该处压力更大;由于受剪切时间更长、更强烈,胶料在挤出段温度最高.最后考察了不同转速下的压力和温度,结果发现挤出过程的最大压力与最高温度均随转速增大而升高,与此同时由于胶料自身的剪切变稀特性和温度依赖性,压力与温度上升的趋势会随着转速的升高而减缓.     

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。     

淀粉基复合发泡材料的加工流变特性及其泡孔形态

以玉米淀粉为基体,辅以相应的增塑剂和发泡剂,利用挤出发泡法制备了淀粉基复合发泡材料。运用双料筒毛细管流变仪研究了甘油增塑剂、NaHCO3发泡剂含量对淀粉基复合发泡材料流变行为的影响。采用扫描电镜（SEM）研究了不同熔体黏度对泡孔形态的影响。结果表明：淀粉基复合发泡材料的熔体流动特性表现为假塑性;随着甘油含量的增加,熔体黏度逐渐下降;随着NaHCO3含量的增加,熔体黏度先下降后提升;随着熔体黏度的降低,熔体内泡孔数量减少,孔径增大,当熔体黏度为1 200 Pa·s时,泡孔大小适中且分布均匀。     

Development of a HPMC-based controlled release formulation with hot melt extrusion (HME)

The objective of this study was to develop hydroxypropyl methylcellulose (HPMC) based controlled release (CR) formulations via hot melt extrusion (HME) with a highly soluble crystalline active pharmaceutical ingredient (API) embedded In the polymer phase. HPMC is considered a challenging CR polymer for extrusion due to its high glass transition temperature (T_g), low degradation temperature, and high viscosity. These problems were partially overcome by plasticizing the HPMC with up to 40% propylene glycol (PG). Theophylline was selected as the model API. By using differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and X-ray powder diffraction (XRPD), the physical properties of the formulations were systematically characterized. Five grades of HPMC (Methocel^®) – E6, K100LV, K4M, K15M, and K100M – were tested. The extrusion trials were conducted on a 16?mm twIn screw extruder with HPMC/PG placebo and formulations containing theophylline/HPMC/PG (30:42:28, w/w/w). The dissolution results showed sustained release profiles without burst release for the HPMC K4M, K15M, and K100M formulations. The extrudates have good dissolution stability after being stressed for 2 weeks under 40°C/75% RH open dish conditions and the crystalline API form did not change upon storage. Overall, the processing windows were established for the HPMC based HME-CR formulations.     

连续挤压铜扁排的阻流角设计及物理场分布

基于Deform-3D平台,建立了Conform连续挤压生产大宽厚比铜扁排有限元模型,研究了连续挤压过程中阻流角变化对模具出口处金属流动及相应应力场分布的影响规律,并结合方差分析法获得了模具出口处的流速均方差,观察模具阻流角对扁排成型的影响.研究表明:模具阻流角从3°~15°变化时,随着阻流角的增加,金属流速均方差先增大后减小,其阻流角区域等效应力值以及模具入口处沿挤压方向应力也逐渐增加;在定径带长度一定以及模具载荷允许的情况下,选择3°、5°、15°的阻流角可使模具出口处金属流速相对稳定,扁排成形性较好;当模具容易损坏时,选择3°和5°阻流角既可降低模具载荷又可获得板形均匀的扁排.     

汽车橡胶密封条挤出口模结构分析及其实验验证

首先通过分析橡胶材料流变实验数据,确定采用Bird-Carreau本构模型;然后应用Polyflow软件对某实际EPDM橡胶密封条产品挤出过程中挤出口模流道结构对挤出的影响进行了有限元分析。结果表明,口模流道某些部位(如窄缝区域)进行适当的加宽有利于使挤出速度及熔体压力分布更均匀,挤出产品形状和实际形状更接近。     

Injection of calcium phosphate pastes: prediction of injection force and comparison with experiments

Calcium phosphate ceramics suspensions (ICPCS) are used in bone and dental surgery as injectable bone substitutes. This ICPCS biomaterial associates biphasic calcium phosphate (BCP) granules with hydroxypropylmethylcellulose (HPMC) polymer. Different ICPCS were prepared and their rheological properties were evaluated in parallel disks geometry as a function of the BCP weight ratio (35, 40, 45 and 50?%). The suspensions show a strongly increased viscosity as compared to the suspending fluid and the high shear rate part of the flow curve can be fitted with a power law model (Ostwald-de Waele model). The fitting parameters depend on the composition of the suspension. A simple device has been used to characterize extrusion of the paste using a disposable syringe fitted with a needle. The injection pressure of four ICPCS formulations was studied under various conditions (needle length and radius and volumetric flow rate), yielding an important set of data. A theoretical approach based on the capillary flow of non-Newtonian fluids was used to predict the necessary pressure for injection, on the basis of flow curves and extrusion conditions. The extrusion pressure calculated from rheological data shows a quantitative agreement with the experimental one for model fluids (Newtonian and HPMC solution) but also for the suspension, when needles with sufficiently large diameters as compared to the size of particles, are used. Depletion and possibly wall slip is encountered in the suspensions when narrower diameters are used, so that the injection pressure is less than that anticipated. However a constant proportionality factor exists between theory and injection experiments. The approach developed in this study can be used to correlate the rheological parameters to the necessary pressure for injection and defines the pertinent experimental conditions to obtain a quantitative agreement between theory and experiments.     

不同熔体流动速率的SA型透明尼龙的流变性能

采用固相后缩聚方法制备了一系列熔体流动速率不同的SA型透明尼龙(SATN),采用毛细管流变仪对其流变性能进行了研究,并讨论了熔体流动速率对其流变性能的影响。研究结果表明,SATN熔体属假塑性流体,表观黏度随着剪切速率的升高而降低;随着熔体流动速率的减小,SATN的非牛顿性增强,熔体黏度增大,对剪切速率的敏感性增强,但是对温度的敏感性减弱。     

啮合异向双螺杆挤出机仿真研究

采用 Solidworks 三维建模软件建立了啮合异向双螺杆螺纹元件与啮 合同向双螺杆螺纹元件的物理模型。运用 Polyflow 软件对聚乳酸流体进行三 维流体仿真,从聚乳酸流体的剪切速率、黏度、压力和速度等 4 个方面,对 比研究啮合异向双螺杆挤出机螺纹元件与啮合同向双螺杆挤出机螺纹元件对 聚乳酸流体的加工效果。研究结果表明,聚乳酸流体在啮合同向双螺杆挤出 机螺纹元件中,受到的剪切速率大、轴向运动速度慢而获得了较好的混合效 果;聚乳酸流体在啮合异向双螺杆挤出机螺纹元件中,轴向流动速度较快, 挤出效果好。