Large‐scale extrusion processing and characterization of hybrid nylon‐6/SiO2 nanocomposites

Solution impregnations, pulltrusion and film stacking are widely used methods to prepare thermoplastic composite materials. Extruders are used to melt the polymer and to incorporate fibers into the polymer in order to modify physical properties. In this article, the compounding of colloidal silica nanoparticles filled polyamide‐6 (PA‐6) is achieved using a twin‐screw extruder, which has a significant market share due to its low cost and easy maintenance. The experiments were performed at 250 rpm and the bulk throughput was 6 kg h^?1 with a pump pressure of 30 bars. The composites were characterized with nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). As determined by WAXD, the PA‐6 showed higher amounts of γ‐phase when compared to other synthesis methods such as in situ polymerization. TEM pictures showed that the silica particles aggregated nevertheless, upon addition of 14% (w/w) silica the E‐modulus increased from 2.7 to 3.9 GPa indicating that an effective mechanical coupling with the polymer was achieved. The behavior, illustrated with dynamic mechanical analysis (DMA) curves, indicated that in general when a filled system is compared to unfilled material, the values of the moduli (E′ and E″) increased and tan δ decreased. Determination of molecular mass distribution of the samples by means of size exclusion chromatography (SEC) coupled to a refractive index (RI), viscosity (DV) and light scattering (LS) detector revealed that the addition of silica did not decrease the average molecular weight of the polymer matrix, which is of importance for composite applications. Copyright © 2004 John Wiley & Sons, Ltd.     

Extrudate swell behavior of PS and LLDPE melts in a dual die with mixed circular/slit flow channels in an extrusion rheometer

Extrudate swell behaviors of polystyrene (PS) and linear low‐density polyethylene (LLDPE) melts in a dual channel die, having mixed circular/slit flow channels, in a constant shear rate rheometer were examined. The extrudate swell ratio for PS melt was observed to be higher than that for LLDPE melt for all cases, this being associated with the differences in molecular structures that could be described in terms of power law indexes and secondary flows near the die entrance. In single channel die, the extrudate swell of both PS and LLDPE melts in circular flow channel die was greater than that in slit flow channel, whereas, in dual channel die the slit channel exhibited a higher extrudate swell ratio, the results being explained by revealing the flow patterns of the melt in the barrel and die of the rheometer. It was found that the dimensionless size of the vortex flows near the entrance, and the extent of disentanglement of molecular chains on entering the die were the important factors for the differences in the extrudate swell ratios of the melts at the die exit influenced by the die designs used. Copyright © 2003 John Wiley & Sons, Ltd.     

锥形模圆柱体超塑性挤压非局部摩擦分析

为了考虑金属材料表面微凸结构对模具与工件接触区域上的非局部摩擦效应,在锥形模圆柱体超塑性挤压加工分析中,采用Oden等提出的非局部摩擦定律代替经典的库仑摩擦定律,利用主应力法或工程法建立了相应问题的积微分形式的力平衡方程.在简化的情况下,采用摄动法求得所论问题的近似解,并分析了影响应力的非局部效应的相关因素.     

Processing polyamides with superheated water

Superheated water (shH₂O) is investigated as a process aid in conventional aliphatic polyamide (PA) systems. The polymers investigated include PA 6 (PA6), PA 6,6 (PA66), PA 6,12 (PA612), and PA 12 (PA12). It is shown that the PA melting and crystallization temperatures are significantly reduced when exposed to shH₂O. For example, the melting temperature of PA6 is depressed from 206 to 153 °C in the presence of shH₂O. A relationship between amide group density and thermal transition temperature reduction is observed. Processing these materials in shH₂O has led to a variety of materials ranging from low‐density foams to higher density locally anisotropic foamed morphologies. In situ observations of PAs melting in the presence of shH₂O are performed using a specially designed reactor. Results from these experiments are used to estimate the diffusion coefficient of shH₂O in PA6. Finally, low‐temperature extrusion is performed with PA6 and shH₂O at temperatures as low as 180 °C and mixture viscosity is estimated. A 20‐fold depression in the melt viscosity of PA6 is observed at 240 °C with shH₂O. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 803–813     

Influence of processing and clay type on nanostructure and stability of polypropylene–clay nanocomposites

Melt processing is a critical step in the manufacture of polymer articles and is even more critical when dealing with inhomogeneous polymer–clay nanocomposites systems. The chemical composition, and in particular the clay type and its organic modification, also plays a major contribution in determining the final properties and in particular the thermal and long-term oxidative stability of the resulting polymer nanocomposites. Proper selection and tuning of the process variable should, in principle, lead to improved characteristics of the fabricated product. With multiphase systems containing inorganic nanoclays, however, this is not straightforward and it is often the case that the process conditions are chosen initially to improve one or more desired properties at the expense of others.     

Chemical modification of poly(lactic acid) and its use as matrix in poly(lactic acid) poly(butylene adipate-co-terephthalate) blends

Poly(lactic acid), PLA, was chemically modified with maleic anhydride (MA) by reactive extrusion. The effect of this modification on molar mass (MM) and acidity was assessed by means of size-exclusion chromatography (SEC) and titration, respectively. PLA MM decreased in the presence of MA solely and of MA and peroxide. Reduction in MM was monitored by the increase in acidity. PLA blends containing poly(butylene adipate-co-terephthalate) (PBAT) were prepared through different mixing protocols, PLA/PBAT, PLA-g-MA/PBAT and PLA/PBAT/MA/peroxide (PLA/PBAT in situ). SEC results and rheological properties revealed reduction in MM and viscosity of the modified blends. PLA/PBAT presented increase in MM and bimodal MM distribution. The calculated interfacial tension was significantly lower for the modified blends, despite the lower average particle area of PLA/PBAT. Surprisingly, the modified blends presented higher yield strength than that predicted by the rule of mixtures, which might indicate interfacial reactions.     

Some effects of foaming of the poly(butylene adipate‐co‐terephthalate) modified by electron radiation

Investigation of the effect of electron radiation and foaming agent on some properties of poly(butylene adipate‐co‐terephthalate) (PBAT) was the aim of the present paper. The mass flow rate, weight‐average molecular weight of irradiated PBAT as well as the morphological structure of foamed samples, their density, tensile strength, and specific strength were determined. It was found that irradiation of PBAT induces growth in weight‐average molecular weight and decrease in mass flow rate, and as a consequence of this increase in viscosity of this polymer. It was also found that foaming of irradiated PBAT causes formation of homogeneous cellular structure or structure with a clear separation of large and small cells. Simultaneously, the irradiated and foamed PBAT shows smaller density than that of non‐irradiated and foamed PBAT. Moreover, electron radiation does not influence tensile strength of the foamed PBAT; however, it increases its specific strength, although only if the content of foaming agent is 1 wt%.     

Melt Extrusion Encapsulation of Flavors: A Review

Encapsulation of flavor and aroma compounds has been largely explored in order to meet appraisal demands from consumers by improving the impact of flavor during the consumption of food products. Even though several techniques have been used for encapsulating volatile compounds, i.e., spray drying, fluidized bed coating, coacervation, and melt extrusion, those most frequently used in the food industry are spray drying and melt extrusion. In this article, the different techniques of encapsulation of flavors and fragrances in polymer-based matrices by extrusion are reviewed and partly re-defined, emphasizing the differences between the various techniques reported so far and the role of matrix types, additives, and operative conditions. Also, the role of water as a key parameter for controlled release and shelf stability of the delivery system will be discussed.     

Novel fabrication of magnetic thermoplastic nanofibers via melt extrusion of immiscible blends

A novel technique of fabricating magnetic thermoplastic nanofibers by the control of the phase separation of immiscible polymer blends during melt extrusion was presented. The magnetic poly(vinyl alcohol‐co‐ethylene) (PVA‐co‐PE)/Fe₃O₄ composite nanofibers were prepared via the melt extrusion of cellulose acetate butyrate matrix and PVA‐co‐PE preloaded with different amounts of Fe₃O₄ nanoparticles. The morphologies of magnetic composite nanofibers were characterized by scanning electron microscopy. The uniform dispersion of Fe₃O₄ nanoparticles in nanofiber matrixes and crystal structures were confirmed using transmission electron microscopy and wide angle X‐ray diffraction. Thermogravimetric analysis was employed to quantify the exact loading amount of Fe₃O₄ nanoparticles in the composite nanofibers. The magnetic measurements showed that composite nanofibers displayed superparamagnetic behavior at room temperature. With increasing content of Fe₃O₄ nanoparticles, the saturation magnetization of the magnetic composite nanofiber significantly improved. The prepared magnetic composite nanofibers might have found potential applications in the sensors and bio‐molecular separation fields. Copyright © 2012 John Wiley & Sons, Ltd.     

Novel Preparation of Polyethylene from Nano‐extrusion Polymerization Inside the Nanochannels of MCM‐41/MgCl2/TiCl4 Catalysts

The MCM‐41 and SiO₂ supported TiCl₄ and TiCl₄/MgCl₂ catalysts with different molar ratios of Mg/Ti were synthesized and used for ethylene polymerization under atmospheric pressure. The nanochannels of MCM‐41 serve as nanoscale polymerization reactor and the polyethylene nanofibers were extruded during the reaction. The nanofibers were observed in SEM micrographs of resulting polyethylene. The effect of MgCl₂ on catalytic activity and thermal properties of resulting polyethylene is investigated too. In the presence of MgCl₂, the catalytic activity increased and more crystalline polyethylene with higher melting points were formed. However, no fibers could be observed in the polyethylene prepared by SiO₂ supported catalysts.