Polystyrene prepared by reactive extrusion: kinetics and effect of processing parameters

The conversion and residence time were investigated during the bulk polymerization of styrene in a twin screw extruder. It was found that polymerization mainly occurred in the zone between 400 and 1000 mm along the screw axis in the extruder, corresponding to the residence time of the reactants ranging from 1 to 4 min in the extruder. Furthermore, the processing conditions (feed rate, screw rotation rate) and average molecular weight of the polymer have a great effect on the residence time. Based on dimensionless analysis, a model of the residence time has been built‐up, which has been confirmed by the results of realistic measurements. A kinetic model of the polymerization has also been established under the assumption that the screw extruder can be regarded as an ideal plug flow reactor. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of the Mixture Composition on Shear and Extensional Rheology of Recycled PET and ABS Nanocomposites

Summary: Recycled PET as well as ABS - organomodified montmorillonite nanocomposites were prepared via melt compounding in a counter-rotating twin screw extruder. The topological changes in polymer matrices as dependency on clay modification have been evaluated from dynamic experiments in the shear flow using low amplitude oscillatory measurements. Flow characteristics of all studied organoclay nanocomposites showed shear-thinning behavior at low frequencies. Filling of PET with some organoclays led to degradation reactions, which were reflected by lower magnitudes of viscosity and storage modulus in the range of higher frequencies as compared to unfilled polymer matrix. On the contrary, no degradation during the processing of different organoclays with recycled ABS has been observed.     

Melt rheology and morphology of binary and ternary PS/HIPS blends for blown film extrusion applications

Rheology is an important tool for evaluating the potential application of a specific material in the production of blow molding films. In the present study, binary and ternary blends based on two different grades of polystyrene (PS) and high impact polystyrene (HIPS) were prepared by melt mixing in a twin screw extruder, using a simplex-centroid mixture design. Rheological analysis was performed based on elongational and dynamic rheology tests combined with scanning electron microscopy. Based on the rheology tests performed, the PS1/HIPS (50:50 wt.%) binary blend is a promising candidate for use in blow molding film applications.     

Effect of the Organoclay Structure on Morphology and Rheological Response of PBT Nanocomposites

In this paper the effect of different organoclays on the structure and the rheological properties of poly(butyleneterephtalate)–clay nanocomposites produced by melt compounding was investigated. The study was carried out using as nanometric fillers four commercial montmorillonites, treated with different organic modifiers and having similar interlayer spacing and organo-modifier concentration. Each organoclay was melt compounded with PBT (at 3%, 6% and 9% by weight of clay) using a twin screw extruder. Using the same processing conditions, hybrid samples containing the unmodified silicate were also prepared for comparison purposes. All the obtained nanocomposite samples were submitted to physico-chemical (XRD, TEM and FT-IR), and rheological measurements in order to evidence the role of polymer-clay affinity on the morphology and on the viscoelastic response of the materials. The results have pointed out that, with the used processing conditions, all nanocomposites exhibit a mixed intercalated/exfoliated structure; nevertheless, the clay dispersion homogeneity and the exfoliation level reached in the samples are higher for Nanofil 919 and Dellite 43B fillers, the organic modifiers of which may favorably interact with PBT matrix.     

Modeling of particle‐dispersed melting mechanism and its application in corotating twin‐screw extrusion

Particle‐dispersed melting is a complex but important melting mechanism in the corotating twin‐screw extruder. In this study, the complex multi‐particle‐dispersed system was simplified into a single‐particle melting model. The finite‐difference method was introduced to solve this problem. The simulation results show that the melting of a particle may involve two steps: the heating stage and melting stage. The heating time and melting time depend on solid concentration, initial melt and solid temperature, and shear rate. Calculations indicate that high solid concentration and solid temperature, low melt temperature and shear rate will result in a more uniform temperature distribution after polymer melting. The model offers valuable information for designing the melting zone in a corotating twin‐screw extruder, especially at high screw speed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2461–2468, 2001     

Polyamide‐6/natural clay mineral nanocomposites prepared by solid‐state shear milling using pan‐mill equipment

The polyamide‐6 (PA6)/natural clay mineral nanocomposites were successfully prepared by solid‐state shear milling method without any treatment of clay mineral and additives. PA6/clay mixture was pan‐milled to produce PA6/clay compounding powder, using pan‐mill equipment. The obtained powder as master batch was diluted with neat PA6 to prepare composites by a twin‐screw extruder. The clay silicate layers were found to be partially exfoliated and dispersed homogeneously at nanometer level in PA6 matrix. The rheological measurements and mechanical properties of nanocomposites were characterized. The shear viscosities of nanocomposites were higher than that of pure PA6, and tensile strength and tensile modulus increased, but Izod impact strength decreased, with increasing concentration of clay. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 249–255, 2006     

Reprocessability and melting behaviour of self-reinforced composites based on PP homo and copolymers

In our present study, the reprocessability of a self-reinforced PP composites (SRPPC) prepared by compression molding was studied. The composite materials (handled separately, based on the related matrix material) were ground, then extruded five times and injection molded after the first and fifth cycle in order to investigate the behaviour of the material during reprocessing. As a reference, the matrices of the composites were also reprocessed and injection molded similarly to the composites. On the manufactured specimens, static (tensile and flexural) and dynamic mechanical tests (Charpy) were performed. The melting and crystalline characteristics were studied by Differential Scanning Calorimetry (DSC). The probable decomposition caused by multiple extrusions was followed by the Melt Volume Rate (MVR). The results indicated that in case of commercial materials there is no significant degradation even after multiple reprocessing cycles; therefore, the reprocessability of SRPPC products has no hindrance. The presence of α-iPP reinforcement in the rPP-based composites after reprocessing results in increased inclination for crystallization and consequently leads to improved mechanical stiffness compared to rPP neat matrices.     

Peroxide‐controlled degradation of poly(propylene): rheological behaviour and process modelling

The control of the molecular weight distribution of poly(propylene) resins by peroxide degradation is widely used in polymer industry. It allows to adjust the viscosity of these resins to the level required for processing applications. The purpose of this work was to characterise the influence of peroxide degradation on the rheological behaviour of an homopolymer PP and a block copolymer PP/PE, and to use these results to obtain a predictive model of the degradation in a twin‐screw extruder. By coupling a thermomechanical model of the twin‐screw extrusion process, a kinetic model of the considered reactions and the rheological behaviour, it was possible to calculate the changes in molecular weight along the extruder, during the peroxide‐controlled degradation.     

Morphologies and properties of plasticized starch/polyamide compatibilized blends

A new sodium carboxymethylcellulose (CMC) compatibilized glycerol-plasticized starch/polyamide PA11 blend having improved mechanical properties was realized in a one step extrusion process. Blends were prepared in internal mixer and twin screw extruder. Mechanical properties (stress and strain at break) are improved by adding 1 wt% of CMC. Rheological characterization and scanning electron microscopy show that a co-continuous morphology is observed on a wide range of TPS amount.     

Synthesis,rheology, and morphology of nylon‐11/layered silicate nanocomposite

Exfoliated nylon‐11/layered silicate nanocomposites were prepared via in situ polymerization by dispersing organoclay in 11‐aminoundecanoic acid monomer. The original clay was modified by a novel method with 11‐aminoundecanoic acid. In situ Fourier transform infrared spectroscopy results show that stronger hydrogen bonds exist between nylon‐11 and organoclay than that of between nylon‐11 and original clay. The linear dynamic viscoelasticity of organoclay nanocomposites was investigated. Before taking rheological measurements, the exfoliated and intercalating structures and the thermal properties were characterized using X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results show that the clay was uniformly distributed in nylon‐11 matrix during in situ polymerization of clay with 4 wt % or less. The presence of clay in nylon‐11 matrix increased the crystallization temperature and the thermal stability of nanocomposites prepared. Rheological properties such as storage modulus, loss modulus, and relative viscosity have close relationship with the dispersion favorably compatible with the organically modified clay. Comparing with neat nylon‐11, the nanocomposites show much higher dynamic modulus and stronger shear thinning behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2161–2172, 2006     

同向啮合双螺杆挤出机挤出过程的计算机模拟

计算机模拟研究了聚苯乙烯在TSE-35A型同向啮合双螺杆挤出机的挤出过程.计算得到不同喂料速率与不同转速下的停留时间分布,并与在线荧光法测量值对比,二者基本相符.确定了停留时间与螺杆转速及喂料速率之间的函数关系式.模拟结果还预测了喂料速率、螺杆转速等工艺参数对双螺杆内流场变量,如温度、填充率、压力及粘度等的影响.模拟计算有助于了解双螺杆挤出机内部聚合物材料流动状态及停留时间长短,从而指导实际聚合物生产.     

Nanomorphology and fire behavior of polystyrene/organoclay nanocomposites containing brominated epoxy and antimony oxide

Organoclay nanocomposites were prepared by ultrasound‐assisted solution intercalation technique based on polystyrene containing brominated epoxy and a combination of brominated epoxy and antimony oxide. Aspects of nanomorphology and nanodispersion were investigated by X‐ray diffraction and transmission electron microscopy whereas flammability and reaction to fire were evaluated using limiting oxygen index, UL‐94, and mass loss calorimeter tests. Polystyrene/brominated‐epoxy‐blend‐based nanocomposites showed mixed intercalated–exfoliated nanomorphology where polymer‐intercalated crystallites predominantly exist in polystyrene matrix and exfoliated silicate layers reside on polystyrene/brominated epoxy phase boundaries and within brominated epoxy domains. Organoclay was found to impart a compatibilization effect on polystyrene and dispersed brominated epoxy, which facilitates uniform distribution of a fine flame‐retarding phase within the matrix. With the reduction of the rate at which decomposition products evolve into the gas phase, organoclay nanocomposites showed notable reductions in peak heat release rate and increases in limiting oxygen index. The gas‐phase hot radical entrapment by halogenated flame‐retardant system was coupled with the condensed‐phase physical action of nanodispersed organoclay, which increased the overall fire‐retardant effectiveness. Fire‐retardant mechanisms of nanocomposites based on polystyrene/brominated epoxy blends were attributed to nanoconfinement and tortuous pathway effects of organoclay rather than to carbonaceous char formation proposed earlier for polystyrene/organoclay systems without conventional flame retardants. Copyright © 2011 John Wiley & Sons, Ltd.     

Modeling of L-lactide Polymerization by Reactive Extrusion

The kinetics of L-lactide ring-opening polymerization initiated by stannous octoate and triphenylphosphine was investigated in a batch apparatus (Haake Rheocord Mixer). Based on the experimental data, a kinetic model is developed, considering a coordination-insertion mechanism. Reactive extrusion experiments were further conducted for the same polymerization process, on a co-rotating twin screw extruder. The melted material flow and mixing was described by using the Ludovic® commercial simulator. Based on the developed kinetic model and simulated flow of L-lactide polymerization mixture, a mathematical model of reactive extrusion process is formulated, describing the evolutions of monomer conversion and average molecular weight along the extruder. The model is predicting with a reasonable good accuracy the experimental data.     

High performance long chain polyamide/calcium silicate whisker nanocomposites and the effective reinforcement mechanism

PA1012/calcium silicate whisker nanocomposites with contents of whisker ranging from 10 wt% to 40 wt%, are prepared by twin screw extruder without any additions of coupling agent. The effect of whisker on the matrix is analyzed by the studies of morphology, the mechanical properties, water absorption and thermal stabilities. SEM micrographs obviously demonstrate, even under the high filler content of 40 wt% and without surface treatment, calcium silicate whisker can be homogeneously dispersed in polyamide, directly leading to the enhanced mechanical properties. The mechanism of higher efficiency of reinforcement is needle-like shape whisker, having access to be intercalated, and mutual affinity caused by hydrogen bonding interaction between carbonyl group in polyamide chain and hydroxyl group in whisker surface. Both aspects attach matrix with excellent stress-transfer properties. In addition, with the assistance of whisker, the nanocomposite favors an improved water absorption as well as thermal stability, which is intimately associated with physical performance.     

In-line monitoring of droplets deformation and recovering and polymer degradation during extrusion

An extruder can be operated as a torque rheometer by setting an external control of the processing variables and adding an in-line optical detector and an on-off mechanical valve at the extruder die exit. Various operational modes can be used including constant, ramp and sinusoidal changes of the die-head pressure. With the valve closed, a fixed amount of polymer is added and the extruder put into operation, controlling the screw rotation speed via software, having a proportional/integral/derivative controller. Polymer degradation can be followed recording changes in barrel pressure and torque. After processing, the valve is opened and the molten polymer discharged under a controlled die-head pressure, manipulating again the screw rotation speed. The polymer mixture morphology can be scanned during the discharge of the melt flow by the in-line turbidimeter, showing the deformation/recovery of the second phase droplets.     

Study on the Effect of Uniaxial Elongational Flow on Polyamide Based Nanocomposites

This work focuses on the study of uniaxial elongational flow and its effects on morphology and stiffness of polyamide-6 based nanocomposites prepared by melt compounding. The elongational flow characterization was realized by converging flow method and fiber spinning technique. During the haul-off tests, fibers of the neat polyamide-6 and the hybrids (at 3 and 6 wt% of silicate) were collected at different draw ratios. Mechanical properties of the produced fibers were investigated and correlated to their nanostructure through analytical techniques sensitive to different aspects of morphology, such as DSC and TEM analysis. Rheological results, obtained with a capillary rheometer, indicate that the shear viscosity decreases with the silicate loading, while the extentional viscosity increases. Moreover, the presence of the silicate in polymer matrix leads to enhancements of draw-down force and reduction of the breaking draw ratio. In hybrid fibers an enhanced degree of exfoliation of the filler was observed upon drawing. Moreover, DSC analyses suggest that the crystalline structure of the fibers is the result of two opposite effects: the presence of the silicate which stabilizes the γ form and the drawing which promotes the α crystal phase. The degree of silicate exfoliation and the amount of the different crystal phases strongly affect the tensile properties of the fibers.     

Re‐Gradation of Photo‐Oxidized Post‐Consumer Greenhouse Films

Summary: The degradation undergone by the polymers during their use and because of the thermo‐mechanical degradation undergone during the reprocessing operations provokes, among other effects, the decrease of the molecular weight. The change of the molecular architecture is responsible for the deterioration of all the properties. In order to restore the properties of post‐consumer recycled plastics, some rebuilding of the molecular structure is necessary. In this work, photo‐oxidized films for greenhouses were reprocessed in presence of additives able to react with the polyethylene in order to form branching and cross‐linking, improving the properties of these post‐consumer plastic.

Pressure as a function of time in the mini twin‐screw extruder, processing speed 70 rpm.     

Thermal stability and water uptake of high performance epoxy layered silicate nanocomposites

Intercalated and ordered exfoliated layered silicate nanocomposites based on three different epoxy resins of different structures and functionalities were synthesized using an octadecyl ammonium modified smectite clay. Water uptake properties of series of each nanocomposite system with different organoclay concentrations were determined by gravimetric measurements over a period of time. The diffusion coefficients were determined and the effect of the absorbed water on the thermal relaxations investigated. The equilibrium water uptake of all nanocomposites was reduced compared to the neat epoxy system but the rate of water diffusion remained unaffected. Further, the thermal stability of the different nanocomposites was determined using thermogravimetric analysis. The nanocomposites showed slightly reduced thermal stability, as indicated by a slight decrease in onset of degradation, whilst the final char concentration increased for greater organoclay concentrations.     

聚丙烯共混物一步法反应共混增容的研究

研究了影响聚丙烯／（丙烯腈 苯乙烯）共聚物（ＰＰ／ＡＳ）合金反应挤出生成的各项因素,发现在过氧化二异丙苯（ＤＣＰ）存在的条件下进行反应共混可以发生接枝反应,生成ＰＰ与ＡＳ的相互接枝物．接枝物的生成显著地细化了分散相粒子,改善了合金相形态．为抑制反应共混过程中聚丙烯的降解,同时促进接枝反应,在ＰＰ／ＡＳ／ＤＣＰ反应共混中加入了含适量双键组分的添加剂亚油酸三甘酯（ＧＴＬ）．结果发现,较少量ＧＴＬ的加入就显著抑制了聚丙烯的降解,且进一步改善了合金的相形态．在合适的ＧＴＬ与ＤＣＰ用量下,反应共混不但显著改善了ＰＰ／ＡＳ合金的相形态,而且提高了合金的力学性能,初步确立了聚丙烯共混物一步反应共混挤出增溶的方法．