Study of crystal structure of (polyvinylidene fluoride/clay) nanocomposite films: Effect of process conditions and clay type

Three Polyvinylidene fluoride (PVDF) different in molecular structure were used to produce nanocomposities films by cast extrusion with a particular emphasis on maximizing the β crystal phase content. The PVDF/clay compounding followed by cast film production was carried out through melt extrusion using a twin screw extruder equipped with a slit die. X‐ray diffraction (XRD) results showed that clay melt intercalation is almost similar for all three PVDFs. The XRD results also revealed that nanocomposite films from PVDF with branched chain structure (PVDFB) generated the greatest amount of β phase. FTIR spectroscopy measurements confirmed the XRD results but also revealed that significant stretching of the melt films at the die or rapid cooling would adversely affect the formation of β phase. The amount of β phase obtained based on nanoclay compounding was compared with that obtained from conventional method: stretching of molded PVDF film with initial α phase. Stretching of PVDF film at 60°C yielded pure β phase that means complete transformation of α to β. From mechanical properties, tensile tests were carried out on PVDF nanocomposite films to evaluate mechanical strength. PVDF with low molecular weight exhibited a very low strain at break while branched PVDF and high molecular weight PVDF could sustain more strain. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Effect of poly(methyl methacrylate) addition on the dielectric and energy storage properties of poly(vinylidene fluoride)

Poly(methyl methacrylate) (PMMA) was introduced into poly(vinylidene fluoride) (PVDF) via a solution blending process, and a series of PVDF/PMMA blends were obtained in an effort to reduce the energy loss of pure PVDF. The effects of the composition and thermal treatment on the properties of the polymer blends were carefully studied. The results show that the introduction of PMMA led to a lower crystallinity and a smaller crystal size of PVDF for its dilution effect. As a result, the dielectric constant and energy storage density of the polymer blends were slightly reduced. Meanwhile, the phase transition of the PVDF crystals from the α phase to the β phase happened during the quenching of the blend melt to ice–water; this was also observed in the untreated or annealed blends with PMMA contents over 50 wt %. Compared with the α‐PVDF, the PVDF crystals in the β phase possessed a lower melting temperature, a higher dielectric constant, and a lower dielectric loss. The addition of PMMA reduced the energy loss of PVDF significantly, whereas the energy storage density decreased slightly. The optimized blend film with about 40 wt % PMMA and PVDF in the β phase showed a relative high energy storage density and the lowest energy loss. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

N-羟甲基丙烯酰胺熔融接枝PP的流变性能

采用熔融接枝法在双螺杆挤出机上制得接枝率为0．20％～0．85％的N-羟甲基丙烯酰胺接枝聚丙烯(PP-g-NHA),讨论了接枝物的组成、剪切应力和剪切速率以及温度对PP-g-NHA熔体流变行为、熔体黏度的影响,测定了接枝物的非牛顿指数。在相同剪切应力时,PP-g-NHA的剪切黏度比PP低,但黏流活化能比PP高。     

Effects of viscosity ratio and compatibilizers on the morphology and mechanical properties of polycarbonate/acrylonitrile-butadiene-styrene blends

A comprehensive experimental study was carried out to investigate the effects of (1) viscosity ratio, (2) temperature on the viscosity ratio, (3) extruder screw location, and (4) compatibilizers on the morphology of bisphenol-A-polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS). Blends were prepared by utilizing a co-rotating twin screw extruder and in-situ morphology obtained via the screw pullout technique. A plot of the PC/ABS viscosity ratio, η_PC/η_ABS, versus the shear rate showed a gradual rise in the curve up to a critical shear rate and thereafter displayed asymptotic character. Contrary to premise, η_PC/η_ABS decreased with increasing temperature. This was elucidated by the melt viscosity of PC being thermally more sensitive than ABS over the temperature range investigated. As expected, the plot of the average domain size versus the viscosity ratio gave a concave up curve with a minimum when the viscosity ratio was close to unity. The morphology evolution along the screw of a twin screw extruder was examined. When sections of the kneading block were examined, the minor phase domains gradually showed reduction in size toward the extruder die, and the samllest domain was realized at the end of the block, namely, the flow impeding left-handed screw element. Polymethylmethacrylate (PMMA) exhibited the greatest ABS domain size reduction, and annealed samples showed that it suppressed coalescence.     

ABS／纳米CaCO3复合材料流变性能的研究

采用双螺杆挤出机，通过熔融共混工艺制备了丙烯腈-丁二烯-苯乙烯共聚物／纳米碳酸钙（ABS／nano-CaCO3）复合材料，利用转矩流变仪研究了其流变行为，探讨了nano-CaCO3用量、剪切速率和温度对复合材料黏度的影响。实验数据显示：ABS／nano-CaCO3熔体为假塑性流体，非牛顿指数n〈1；适量加入nano-CaCO3使复合体系熔体的n值增加，“柱塞流动”现象降低；在低剪切速率下，ABS／nano-CaCO3复合体系的熔体黏度较纯ABS熔体低；在高剪切速率下,复合体系的熔体黏度较纯ABS熔体高。     

Formation and morphology development of poly(butylene terephthalate) nanofibers from poly(butylene terephthalate)/cellulose acetate butyrate immiscible blends

Nano‐scale poly(butylene terephthalate) (PBT) fibers were prepared from PBT/cellulose acetate butyrate (CAB) immiscible polymer blends due to in situ microfibrillar formation during a melt extruding process. The morphological development of the dispersed phase was studied with samples collected at different zones in a twin screw extruder. It was found that the holistic developmental trends of PBT dispersed phase were nearly the same. Fibers began to form even under the shear flow of the twin‐screw extruder. The morphology developmental mechanism of the dispersed phase involved the formation of sheets, holes and network structures, then the size reduction and formation of nanofibers. The effect of viscosity ratio, blend ratio, and shear rate on the morphology evolution was also studied by analyzing the shape and size distribution of the samples. The diameter distribution of the nanofibers could be affected by viscosity ratio, blend ratio, and shear rate. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Non-Newtonian and non-isothermal analysis of flow during polymerization of methyl methacrylate in a model twin screw extruder. Part II

The flow analysis network (FAN) method was modified to analyze the flow during polymerization of methyl methacrylate (MMA) in a model counter-rotating nonintermeshing screw extruder. The shear viscosity of the reactive mixture in the twin screw extruder was considered as a mixture of polymer and monomer. Thus, the reaction viscosity of the mixture of polymer and monomer was taken to be an explicit function dependent on the shear rate, temperature, conversion, and molecular weight. A new flow path method was developed to calculate the residence time distribution, which related to the degree of conversion. The numerical prediction of the velocity, temperature, viscosity, and pressure profiles during reaction in the model twin screw extruder is described.     

Effect of supercritical carbon dioxide on morphology development during polymer blending

Supercritical carbon dioxide (scCO₂) was added during compounding of polystyrene and poly(methyl methacrylate) (PMMA) and the resulting morphology development was observed. The compounding took place in a twin screw extruder and a high‐pressure batch mixer. Viscosity reduction of PMMA and polystyrene were measured using a slit die rheometer attached to the twin screw extruder. Carbon dioxide was added at 0.5, 1.0, 2.0 and 3.0 wt% based on polymer melt flow rates. A viscosity reduction of up to 80% was seen with PMMA and up to 70% with polystyrene. A sharp decrease in the size of the minor (dispersed) phase was observed near the injection point of CO₂ in the twin screw extruder for blends with a viscosity ratio, ηPMMA/ηpolystyrene, of 7.3, at a shear rate of 100 s^?1. However, further compounding led to coalescence of the dispersed phase. Adding scCO₂ did not change the path of morphology development; however, the final domain size was smaller. In both batch and continuous blending, de‐mixing occurred upon CO₂ venting. The reduction in size of the PMMA phase was lost after CO₂ venting. The resulting morphology was similar to that without the addition of CO₂. Adding small amounts of fillers (e.g. carbon black, calcium carbonate, or nano‐clay particles) tended to prevent the de‐mixing of the polymer blend system when the CO₂ was released. For blends with a viscosity ratio of 1.3, at a shear rate of 100 s^?1, the addition of scCO₂ only slightly reduced the domain size of the minor phase.     

Melt flow behavior in capillary extrusion of nanosized calcium carbonate‐filled poly(L‐lactic acid) biocomposites

Nanosized calcium carbonate (nano‐CaCO₃)‐filled poly‐L ‐lactide (PLLA) biocomposites were compounded by using a twin‐screw extruder. The melt flow behavior of the composites, including their entry pressure drop, melt shear flow curves, and melt shear viscosity were measured through a capillary rheometer operated at a temperature range of 170–200°C and shear rates of 50–10³ s^?1. The entry pressure drop showed a nonlinear increase with increasing shear stress and reached a minimum for the filler weight fraction of 2% owing to the “bearing effect” of the nanometer particles in the polymer matrix melt. The melt shear flow roughly followed the power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Hence, adding a small amount of nano‐CaCO₃ into the PLLA could improve the melt flow behavior of the composite. POLYM. ENG. SCI., 52:1839–1844, 2012. © 2012 Society of Plastics Engineers     

同向旋转双螺杆挤出机计量段中聚合物挤出的模拟

建立了非牛顿粘性聚合物熔体在同向旋转双螺杆挤出机计量段中的三维 非等温流动模型,利用网络叠合技术分析挤出机计量段内速度、温度、压力、粘度、粘性耗散热的分布以及螺杆转速、轴向压差对挤出量的影响。     

Melt spinning of PVDF fibers with enhanced β phase structure

Polyvinylidene fluoride (PVDF) fibers with a high amount of β phase crystal structure were prepared by melt spinning. With this technique, the cold drawing process is critical and efficient when aiming for a high amount of β phase. During the cold drawing process, more than 80% of the originally formed α phase crystal structure was converted into the β phase structure. In addition, the incorporation of 0.01 wt % of amino‐modified double wall carbon nanotube (NH₂‐DWCNT) could further enhance the β phase content in the PVDF fibers. FTIR and DSC studies showed that the addition of NH₂‐DWCNT to PVDF fibers could increase both the total crystallinity and β phase fraction in PVDF. The addition of nanoclay was found to be less efficient in this respect. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2603–2609, 2013     

Processing of polypropylene–clay nanocomposites: Single‐screw extrusion with in‐line supercritical carbon dioxide feed versus twin‐screw extrusion

This work investigates two different melt‐blending strategies for preparing compatibilized polypropylene‐clay nanocomposites, specifically: (1) conventional twin‐screw extrusion, and (2) single‐screw extrusion capable of direct supercritical carbon dioxide (scCO₂) feed to the extruder barrel. Proportional amounts (3 : 1) of maleic anhydride functionalized polypropylene compatibilizer and organically modified montmorillonite clay at clay loadings of 1, 3, and 5 wt % are melt‐blended with a polypropylene homopolymer using the two approaches. The basal spacing, degree of exfoliation, and dispersion of organoclay is assessed using X‐ray diffraction, transmission electron microscopy, and rheology. In terms of the latter, both steady shear and small‐amplitude oscillatory shear provide information about the apparent yield stress and solid‐like terminal behavior respectively. Finally, nanoindentation is performed to determine the room temperature modulus of each melt‐blended nanocomposite. The results reveal unequivocally that the high shear of the twin‐screw process is vastly superior to the single‐screw with in‐line scCO₂ addition in generating well‐exfoliated, percolated polypropylene‐clay nanocomposites. It is likely that increased contact time between clay and scCO₂ is necessary for scCO₂ to positively affect exfoliation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 884–892, 2007     

Functionalization of ethylene–propylene–diene monomer rubber with maleic anhydride in the melt state through high‐shear stress‐induced initiation

The functionalization reactions of ethylene–propylene–diene monomer rubber (EPDM) with maleic anhydride (MAH) in melt state through high‐shear‐stress‐induced initiation by an increase in the screw rotation speed of the twin‐screw extruder and through compounded initiation by the addition of some initiator and an increase in the screw rotation speed were investigated. The results show that, with increasing screw rotation speed and reaction temperature, the percentage grafting and melt flow rate of the functionalized products (EPDM‐g‐MAH) were noticeably increased, and the viscosity‐average molecular weight decreased, which implied that the grafting reaction consisted of the chain scission and grafting reaction of the produced macroradicals with MAH. In the presence of a certain peroxide initiator, the crosslinking reaction during melt extrusion was suppressed by an increase in the screw rotation speed. The percentage grafting of EPDM‐g‐MAH amounted to 1.1%, its melt flow rate was between 0.3 and 4.0 g/10 min, and its gel content was less than 1.0%, depending on the screw rotation speed and reaction temperature. Impact testing and scanning electron microscopy showed that the functionalized product prepared through the high shear stress‐induced initiation had a higher blocking activity with the amide terminated of PA66 than that prepared through the peroxide initiation or through the compound initiation, and the impact strength of the PA66/EPDM blends, improved by the high‐shear‐stress‐induced product was noticeably higher than those of the peroxide‐initiated product or the compound‐initiated one. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of the addition of a liquid crystalline copolyester to polystyrenes on blending torque and mechanical properties of blends

Blending of polystyrenes (PS) with a thermotropic liquid crystalline polymer (LCP) was performed by using a continuous corotating twin screw extruder. The influence of LCP content on the blending process was studied by changing the barrel heater temperature and the screw speed. The torque of screw shafts, generated during the blending process, was influenced by LCP content and its influence was not simple. The torque generated during the blending process was not directly related to the apparent melt viscosity of blends. Further, the effects of the matrix viscosity on the morphology and mechanical properties of the PS/LCP blends were studied using three grades of PS as matrix resins. It was found that the size of the LCP dispersed phase decreased with increasing matrix viscosity. Consequently, the mechanical properties of the PS/LCP blend were improved. © 1993 John Wiley & Sons, Inc.     

Styrene grafting onto a polyolefin in an internal mixer and a twin‐screw extruder: Experiment and kinetic model

There has been relatively little effort to quantitatively understand graft copolymerizaution in either batch mixers or twin‐screw extruders. Most efforts have concentrated on grafting maleic anhydride, which does not homopolymerize. In this paper we consider grafting with styrene, which may homopolymerize as well as graft. The influence of residence time on degree of grafting in an internal mixer and a twin‐screw extruder were studied by measuring reaction yields with respect to reaction time in a mixer and along the screw axis in a twin‐screw extruder. The degree of grafting increased with initial monomer and peroxide concentration. Grafting reactions with three different peroxides were also investigated. The degree of styrene grafting in an internal mixer is slightly higher than that in a twin‐screw extruder. The rate of reaction along the screw axis in terms of residence time seems higher than for the batch mixer. The melt viscosity dropped dramatically with addition of peroxide. A kinetic scheme is proposed and the experimental results are critically compared with it.     

双螺杆挤出机螺杆组合对聚丙烯/纳米CaCO3复合材料在线流变性能的影响

采用啮合型同向旋转双螺杆挤出机制备聚丙烯(PP)/纳米碳酸钙(nano-CaCO3)复合材料,制备过程中在双螺杆挤出机末端连接Haake在线流变仪进行在线流变性能测试。研究了两种螺杆组合结构、纳米CaCO3含量对PP/纳米CaCO3复合材料在线剪切黏度的影响,比较了在不同聚合物加工流场下PP/纳米CaCO3复合材料的在线流变性能。结果表明,引入分布混炼有利于降低复合材料的剪切黏度,复合材料剪切黏度随纳米粒子的加入先呈下降趋势,当达到某一含量后,再提高纳米粒子含量会使黏度提高。     

Rheological study of polypropylene copolymer/polyolefinic elastomer blends

Blends of polypropylene copolymer (PP‐cp) and a polyolefinic elastomer (POE) were prepared by a melt‐blending process at 210°C and 60 rpm using a counterrotating twin‐screw extruder. The POE content was varied up to 25%. The shear viscosity over a wide range of shear rate was measured. All blend compositions showed well‐defined zero shear viscosity and shear thinning behavior. The melt viscosity values were between those of the principal components in all cases. Rheology of blends shows different behavior up to concentrations of POE corresponding to the tough–brittle transition. The linear viscoelastic properties (G′, G″, η*, η′, η″) were used to check the miscibility of the two components in the melt state. All blend compositions showed a good degree of miscibility over the range of POE concentrations studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 665–671, 2002; DOI 10.1002/app.10376     

Effect of processing conditions on morphology and mechanical properties of compatibilized polypropylene nanocomposites

This work focuses on the influence of processing conditions on the nanocomposites structure, i.e. intercalated or exfoliated, and on the enhancement of mechanical properties of polypropylene (PP) nanocomposites. These nanocomposites were prepared using the melt intercalation technique in a co-rotating intermeshing twin screw extruder. In order to optimise processing conditions, both screw speed and barrel temperature profile were changed. The role of the compatibilizer (maleic anhydride grafted polypropylene) was also studied. The results obtained show that the barrel temperature is a very important parameter: using lower processing temperature, the apparent melt viscosity and, consequently, the shear stress are higher and, therefore, the exfoliation of the clay is promoted. Even using optimised processing conditions, exfoliation of clay can be achieved only when an high compatibility between polymer and clay exists: the PP nanocomposites containing maleic anhydride show an exfoliated structure and a sensible enhancement of mechanical properties while PP nanocomposites without compatibilizer show a structure mainly intercalated and a lower improvement of mechanical properties.     

啮合同向双螺杆挤出过程轴向循环流道三维流场分析—轴向循环流场分析（Ⅱ）

介绍了作者在啮合同向双螺杆某一轴向位置设置一非啮合段（且该段其中一根螺杆是反向螺纹元件）,从而将轴向循环流动的概念引入到啮合同向双螺杆挤出过程中,并利用ANSYS有限元分析软件对啮合同向双螺杆挤出过程轴向循环流道中的非牛顿流体等温流动进行了三维模拟分析。在得出速度场和压力场的基础上,还对剪切速率、剪切应力及剪切粘度进行了模拟,并将各模拟结果与未引入轴向循环流的啮合同双螺杆挤出过程常规螺纹元件流道的模拟结果进行了比较。     

ABS/PS共混改性研究

采用在材料熔融挤出共混过程中提高双螺杆挤出机螺杆转速的方法,研究了较高螺杆转速条件下双螺杆挤出机的机械剪切应力和弹性体的种类、用量等因素对丙烯腈-丁二烯-苯乙烯共聚物(ABS)/聚苯乙烯(PS)共混材料力学性能和加工流动性能的影响。结果表明,双螺杆挤出机的高剪切应力可促进分散相颗粒的分散和界面结合力的增强,引起共混材料力学性能和熔体流动速率的改善。丁腈橡胶(NBR)粉末对ABS/PS共混材料具有增容增韧作用,挤出共混温度为220℃,螺杆转速在720 r/min,NBR粉末质量分数为10%时,ABS/PS共混材料的缺口冲击强度为16.4 kJ/m2,比改性前约提高1.6倍,达到ABS树脂冲击韧性的指标,并保持了良好的加工流动性。