Numerical simulation of polymer foaming process in extrusion flow

Computer simulations of polymer foaming processes in extrusion flow have been carried out in order to improve current understanding of viscoelasticity and bubble growth effects on die-swelling in the production of polymer foam. The linear and non-linear viscoelastic materials functions of a commercial low density polyethylene (LDPE) melt have been extracted by fitting its rheometric data with constitutive models including a simple viscoelastic model (SVM), the exponential Phan-Thien–Tanner (EPTT) model and the double convected pom–pom (DCPP) model. Simulations of LDPE melt under extrusion flow without foaming show that the predictions of the die-swell by the SVM are in reasonably good agreement with the results obtained from the EPTT and DCPP models. By comparison of the simulation results of LDPE foaming in extrusion flow using the Bird–Carreau model and the SVM, a cooperative effect of polymer viscoelasticity and bubble growth on the die-swell has been quantified. The numerical results also show that the density of polymeric foam decreases significantly with the increasing concentration of foaming agent, and that the combination of the SVM and bubble growth model can account for some essential physics of polymer foaming process in extrusion flow.     

单甘脂对聚苯乙烯挤出发泡性能的影响

利用超临界二氧化碳挤出发泡法,研究了单硬脂酸甘油脂（GMS）母粒的添加量对聚苯乙烯（PS）发泡性能的影响。采用毛细管流变仪研究了GMS添加量对PS/GMS体系的流变特性的影响,观察并测试了发泡材料的微观泡孔结构。研究结果表明,GMS的添加会降低树脂的黏度。母粒中含有的多组分GMS和少组分乙烯-醋酸乙烯（EVA）共同影响制品的表观密度、平均泡孔直径和泡孔密度等参数。在GMS添加量为1.05%,EVA添加量为0.45%时,制品的平均泡孔直径最小,泡孔密度最大。     

Expansion characteristics of thermally expandable microcapsules for dismantlable adhesive under hydrostatic pressure or in resin

ABSTRACT

The expansion characteristics of thermally expandable microcapsules (TEMs) under hydrostatic pressure or in resin were experimentally investigated. For the experiments, the expansion of the microcapsules was observed in high-pressure nitrogen at high temperature utilizing optical microscopy with a digital camera installed. The TEMs used for the experiments were expanded by heating under hydrostatic pressure up to 3 MPa, but the expansion degree decreased with increasing pressure. A cured bulk specimen of epoxy resin containing the microcapsules was made, and the expansion of the microcapsules was again observed with the microscope. It was found that the expansion of the microcapsules in the resin was saturated at a certain temperature. The stress distribution in the resin produced by the expansion of the microcapsules was calculated by the finite-element method. It was found that normal stress occurred, but it was mainly compressive. Tensile stress was also generated, although the maximum value was smaller than that of shear stress. It was observed that the expansion of the microcapsules was limited when there were many microcapsules in the vicinity of the interface. In other words, a complicated stress state occurred, inducing interfacial failure along the interface.     

Numerical study of nonisothermal polymer extrusion flow with a differential viscoelastic model

A numerical study of nonisothermal viscoelastic flow is conducted to investigate the complex flow characteristics of polymer melts in the extrusion process. A general thermodynamic model for the energy conversion related to viscoelastic fluid flow is introduced. The mathematical model for three‐dimensional nonisothermal viscoelastic flow of the polymer melts obeying a differential constitutive equation (Phan‐Thien and Tanner model) is established. A decoupled algorithm based on the penalty finite element method is performed on the calculation. The discrete elastic‐viscous split stress (DEVSS) algorithm, incorporating the streamline‐upwind Petrov‐Galerkin (SUPG) scheme is employed to improve the computation stability. Essential flow characteristics of polymer melts in the extrusion die for hollow square plastic profile is investigated based on the proposed numerical scheme with ignoring the outer thermal resource. The energy partitioning, which quantified the conversion of mechanical energy into thermal energy, is discussed. The effects of volume flow rate and die contraction angle upon the flow patterns are further investigated. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

热膨胀微胶囊的制备研究

以丙烯腈(AN)、甲基丙烯酸甲酯(MMA)、丙烯酸甲酯(MA)为单体,采用悬浮聚合的方法制备了热膨胀微胶囊。通过热膨胀仪、扫描电子显微镜、热重分析仪等分析方法,考察了单体配比、发泡剂种类、反应压力、异戊烷用量和粒径大小对微胶囊发泡性能的影响。结果表明,当丙烯腈(AN)、甲基丙烯酸甲酯(MMA)、丙烯酸甲酯(MA)的摩尔比为12:4:1时,微胶囊的膨胀性能最佳;异戊烷、正己烷、异辛烷作为发泡剂,所制备微胶囊发泡性能优异;异戊烷作为发泡剂时,需加压反应,当加入量为30%时,膨胀性能最佳。     

基于可压缩气辅的聚合物挤出成型非等温黏弹数值分析

基于气体具有可压缩性特点提出了可压缩气辅挤出概念,为探明气辅挤出中可压缩气体对聚合物熔体挤出成型的影响建立了熔体和压缩气体两相流模型,利用有限元计算方法对可压缩气辅的聚合物挤出成型进行了非等温黏弹数值模拟,并对比分析了传统无气辅和可压缩气辅挤出的物理场分布情况。研究表明,气辅挤出中的气体密度分布不是恒定值,而是随压力和温度空间分布变化,并且在引入气体层以及气体可压缩性后,可压缩气辅挤出与传统无气辅挤出方法相比在各物理场分布上存在较大的差异,当可压缩气体入口压力逐渐增大时熔体挤出收缩程度明显增大。该结果与实验一致,这些是传统无气辅挤出模拟无法体现出来的。     

Some viscoelastic properties of ABS polymer

The discrete relaxation spectrum of an ABS (acrylonitrile–butadiene–styrene) polymer at 190°C. was calculated by using results from tensile relaxation moduli and the principle of reduced variables. The shift factor was found to conform well to the WLF equation, and the free volume fraction at T_g was calculated to be 0.026 in good agreement with the universal value. The values of the thermal expansion coefficient of free volume were calculated to be 9.8 X 10^-4 deg.^?1 and 7.0 × 10^?4 deg.^?1, respectively, from the WLF coefficients and from dilatometric results. The width of the entanglement plateau of the relaxation spectrum was observed to be a factor of approximately 2 larger than that calculated from molecular weights between entanglement couplings determined either from rubber elasticity theory or from an assumed molecular model which discounts the presence of the butadiene in the ABS system. By using Pao's theory, flow curves at 190°C. were calculated both from the discrete relaxation spectrum and from the dynamic modulus. These curves were essentially identical. However, the stress values of these curves were found to be about a decade higher than those experimentally determined from capillary flow measurements. Nevertheless, the shapes of the curves are in good agreement, and an explanation is suggested for existing discrepancies. Flow instability, processing variables, and residual strains are discussed in light of the flow curves and the calculated recoverable shear strains.     

Effect of polytetrafluoroethylene on the foaming behaviors of linear polypropylene in continuous extrusion

Linear polypropylene (PP) foams, blown in the continuous extrusion process using supercritical CO₂ as the blowing agent, exhibited poor cell morphology and narrow foaming window, because of their low melt strength. In this study, polytetrafluoroethylene (PTFE) was blended with PP resin with the aim of improving the foaming behavior of PP. It was found that the PTFE particles were deformed into fine fibers under shear or extensional flows during the extrusion process, which significantly increased the melt strength of PP from 0.005 N to 0.03 N (PP/PTFE with PTFE content of 4.0 wt %) at 230°C. The experimental results indicated that the presence of PTFE improved the cell morphology of PP foams and broadened the foaming window of PP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication of thermally expandable core–shell microcapsules using organic and inorganic stabilizers and their application

Thermally expandable core–shell microcapsules (TEM) were fabricated with an organic steric stabilizer and an inorganic Pickering emulsifier. In order to fabricate a TEM, acrylonitrile (AN) and metacrylonitrile (MAN) were used as monomers. Halloysite nanotubes (HNTs) and poly(vinylpyrrolidone) (PVP) were used as the inorganic Pickering emulsifier and the organic stabilizer, respectively. The liquid hydrocarbon content in the core, and the thermal and expansion properties, of TEMs with two different emulsifiers were compared. The mechanical properties of polypropylene (PP) foams containing TEMs prepared with two types of stabilizers were analyzed. The TEMs polymerized with PVP showed a finer expanded cell, while those fabricated with HNTs resulted in a larger expanded cell in the PP matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44247.     

Effect of microcellular foaming on the fracture behavior of ABS polymer

In this work, the properties of microcellular ABS were studied. Foamed samples exhibited a solid skin/foamed core structure, with some elongated cells in the flow direction, while spherical cells were mostly observed in the transversal direction. The flexural modulus, flexural strength, and fracture toughness K_Ic decreased with the density. However, the Crack Tip Opening Displacement (CTOD) was found to increase with the foaming ratio. The evolution of the mechanical properties and fracture toughness was well described by prediction models considering the skin/core morphology of these microcellular materials. Foaming increased the anisotropic behavior of the material, due to the cell elongation caused by the fountain flow during injection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43010.     

Effect of extrusion screw type on properties of recycled glass fiber reinforced liquid crystalline polymer

In this work, when glass fiber reinforced liquid crystalline polymer (GFLCP) was subjected to injection molding once, the recycled GFLCP (RGFLCP) including the scraps and unqualified injection products was granulated by different extruders with varying screw configurations. The glass fibers were observed by SEM and their lengths were calculated by mathematical statistics. In the case of the samples prepared by a single‐screw extruder, the average glass fiber length ( ) and the percentage of glass fibers whose length was higher than critical length (V_j) gradually decreased with the increase of the screw diameter and the ratio of its length to diameter (L/D). However, a drastic reduction of and V_j was observed for the RGFLCP extruded by a twin‐screw extruder. The mechanical, thermal properties, and the shear viscosity of the extruded RGFLCP decreased with the reduction of and V_j. The extruded RGFLCP prepared with a single screw extruder that was featured with 30 mm screw diameter and 30 L/D obtained the excellent properties with a notched impact strength of 103.4 J/m, tensile strength of 110.2 MPa, and flexural strength of 159.3 MPa. Its initial decomposition temperature (T_−1%) and heat distortion temperature were 483.1°C and 256.4°C, respectively. POLYM. COMPOS., 37:370–378, 2016. © 2014 Society of Plastics Engineers     

Effect of fiber orientation on viscoelastic properties of polymer matrix composites subjected to thermal cycles

Fibers in polymer composites can be designed in various orientations for their usage in service life. Various fiber orientated polymer composites, which are used in aeroplane and aerospace applications, are frequently subjected to thermal cycles because of the changes in body temperatures at a range of −60 to 150°C during flights. It is an important subject to investigate the visco‐elastic properties of the thermal cycled polymer composite materials which have various fiber orientations during service life. Continuous fiber reinforced composites with a various fiber orientations are subjected to 1,000 thermal cycles between the temperatures of 0 and 100°C. Dynamic mechanic thermal analysis (DMTA) experiments are carried out by TA Q800 type equipment. The changes in glass transition temperature (T_g), storage modulus (E′), loss modulus (E′′) and loss factor (tan δ) are inspected as a function of thermal cycles for different fiber orientations. It was observed that thermal and dynamic mechanical properties of the polymer composites were remarkably changed by thermal cycles. It was also determined that the composites with [45°/−45°]_s fiber orientation presented the lowest dynamic mechanical properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

On‐line NIR sensing of CO2 concentration for polymer extrusion foaming processes

An on‐line sensor using near infrared (NIR) spectroscopy is developed for monitoring CO₂ concentration in polymeric extrusion foaming processes. NIR absorption spectra are acquired by a probe installed at the foaming extruder die. The calibration curve relating the absorbance spectrum at 2019 nm to the dissolved gas concentration is derived so as to infer dissolved CO₂ gas concentration on‐line from measured NIR spectra. Experimental results show the developed on‐line NIR sensor can successfully estimate dissolved CO₂ concentration in the molten polymer and illustrate that the developed NIR sensing technique is among the more promising methods for quality control of polymeric extrusion foaming processes.     

Relation between the viscoelastic and flammability properties of polymer nanocomposites

Previous work has shown that the formation of a network structure of nanoparticles within a polymer matrix can significantly reduce nanocomposite flammability and that viscoelastic properties could be utilized to predict their flammability reduction. The present work extends this type of investigation to the study of clay and carbon nanotube nanocomposites. In particular, we study PS/clay, PS/MWNT, PMMA/clay, and PMMA/SWNT nanocomposites. At a clay level of about 10% by mass, the network structure is formed for the PS and the PMMA clay nanocomposites; it requires a level of about 0.5% with the SWNT and 2% with the MWNT. These samples showed significantly reduced mass loss rates of PS and PMMA. However, the solid residues collected from radiative gasification tests of PS/clay and PMMA/clay showed many small cracks, despite the network formation within the initial sample. This is in contrast to the smooth, continuous residues (no cracks or openings) for PS/MWNT and PMMA/SWNT nanocomposites. The cracks in the clay samples are probably formed due to weaker network at elevated temperatures due to weaker bridging interaction between clay platelets as compared to stronger network resulting from dense entanglement and bridging of carbon nanotubes.     

Effect of dispersed phase on the morphology of in situ microfibrils and the viscoelastic properties of its composite via direct extrusion

A triangle arrayed triple‐screw extruder was used to prepare in situ polypropylene (PP) microfibrillar composites (MFCs) by direct extrusion, in which polyamide 6,6 (PA66) and poly(butylene terephthalate) (PBT) were used as dispersed phases while PP as matrix phase. The morphological evolution of the dispersed phase were investigated by SEM through taking samples along the extruder from different positions. The results showed that the fibrillating mechanism of PA66 was entirely different from that of PBT. Dynamic oscillatory shear rheological properties were used to analyze the effect of different types of in situ microfibrils on the rheological properties of MFCs. The obtained results showed that the storage modulus and complex viscosity of both PP/PA66 and PP/PBT MFCs were improved with increasing fibrillar aspect ratios. The loss tangent tan δ at low frequencies decreased with the increase of fibrillar aspect ratio. Moreover, the gel point concentration of PP/PA66 composite was lower than that of PP/PBT composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46286.     

Development of an extrusion die with rollers for foaming polymers

Ideas concerning the use of a flat slot die with rollers in the technology of extrusion foaming of polymers are developed. Based on the experimental study of low‐density polyethylene foaming with isobutane, dependences of the cell density and foam density on the polymer solution viscosity, gap width between rollers, die temperature, and talc concentration have been analyzed. A model is formulated for estimating the intensity of coalescence of supercritical bubbles in an inhomogeneous field of flow velocities. The number density of supercritical nuclei formed in a polymer–gas solution in the limiting case of high pressure drop rate is estimated. The obtained simple estimations allow the results of experiments to be justified on a qualitative level. POLYM. ENG. SCI., 55:2256–2269, 2015. © 2015 Society of Plastics Engineers     

Influence of molecular weight distribution on the linear viscoelastic properties of polymer blends

Literature data for the dynamic viscoelastic properties of binary blends of nearly monodisperse polybutadienes, polystyrenes, and poly(methyl methacrylate)s was analyzed using logarithmic plots of dynamic storage modulus G′ versus loss modulus G″, based on a recent theoretical study by Han and John.²⁸ It has been found that for binary blends of monodisperse polymers with molecular weights M much greater than the entanglement molecular weight M_e, the value of G′ in log G′ ? log G″ plots becomes independent of molecular weight, increases sharply as small amounts of a high-molecular-weight component are added to a low-molecular-weight component, and passes through a maximum G′_max at a critical blend composition (?₂)_max, and that G′_max becomes larger and (?₂)_max becomes smaller as the ratio of component molecular weights increases. However, as the molecular weight distribution of the constituent components becomes broader, the effect of blend composition on G′ in log G′ ? log G″ plots becomes less pronounced. This observation has enabled us to explain why log G′ ? log G″ plots of binary blends of commercial polymers, namely, blends of two low-density polyethylenes, blends of poly(?-caprolactone) and poly(styrene-co-acrylonitrile), and blends of poly(methyl methacrylate) and poly(vinylidene fluoride), all having broad molecular weight distributions, give rise to values of G′ between those of the constituent components. When one of the constituent components has molecular weight smaller than M_e, while the other has molecular weight larger, and as small amounts of the high-molecular-weight component are added to the low-molecular-weight component, log G′ ? log G″ plots of binary blends give rise to values of G′ larger than those of the constituent components at low values of G″, but approaches the value of G′ for the low-molecular-weight component as the value of G″ is increased. However as the amount of the high-molecular-weight component is increased above a certain critical composition, binary blends give rise to values of G′ close to that of the high-molecular-weight component at all values of G″. The experimentally observed dependence of G′ on blend composition in log G′ ? log G″ plots is favorably compared to the theoretical prediction of a blending law proposed by Montfort and co-workers.^14,15     

New challenges in polymer foaming: A review of extrusion processes assisted by supercritical carbon dioxide

It is well known that supercritical carbon dioxide (sc-CO₂) is soluble in molten polymers and acts as a plasticizer. The dissolution of sc-CO₂ leads to a decrease in the viscosity of the liquid polymer, the melting point and the glass transition temperature. These properties have been used in several particle generation processes such as PGSS (particles from gas saturated solutions).It is therefore highly likely that extrusion processes would benefit from the use of sc-CO₂ since the rationale of the extrusion processes is to formulate, texture and shape molten polymers by forcing them through a die. Combining these two technologies, extrusion and supercritical fluids, could open up new applications in extrusion.The main advantage of introducing sc-CO₂ in the barrel of an extruder is its function as a plasticizer, which allows the processing of molecules which would otherwise be too fragile to withstand the mechanical stresses and the operating temperatures of a standard extrusion process. In addition, the dissolved CO₂ acts as a foaming agent during expansion through the die. It is therefore possible to control pore generation and growth by controlling the operating conditions.This review focuses on experimental work carried out using continuous extrusion. A continuous process is more economically favourable than batch foaming processes because it is easier to control, has a higher throughput and is very versatile in the properties and shapes of the products obtained.The coupling of extrusion and supercritical CO₂ technologies has already broadened the range of application of extrusion processes. The first applications were developed for the agro-food industry 20 years ago. However, most thermoplastics could potentially be submitted to sc-CO₂-assisted extrusion, opening new challenging opportunities, particularly in the field of pharmaceutical applications.This coupled technology is however still very new and further developments of both experimental and modelling studies will be necessary to gain better theoretical understanding and technical expertise prior to industrial use, especially in the pharmaceutical field.     

Phase inversion and viscoelastic properties of phase-separated polymer blends

Summary The morphologies and viscoelastic properties of the phase-separated poly(styrene-co-maleic anhydride)/poly(methyl methacrylate) bends have been investigated using TEM and rotational rheometry. Various rheological criteria based on the viscoelastic properties of the blends have been used to evaluate the phase inversion. By correlating the rheological results to data from morphological analysis by TEM, it is found that the maximum of the storage modulus and the viscosity at low shear rate are most suitable for determining the phase-inversion composition of the present phase-separated polymer blends. While the data from the maximum of the shear viscosity at high shear rate and from the shear-thinning extent proposed by Ziegler et al. slightly deviate from that from TEM micrograph, which indicates that shear-induced structure lie. Moreover, the prediction using various rheological models, as the viscosity ratio of the two coexisting phases is substituted for that of the pure components, is in nearly good agreement with that from TEM observation.     

硫化体系对再生胶发泡性能的影响

采用跳模法对再生胶进行发泡,考察了硫黄、促进剂CZ、TMTD对再生胶发泡特性及发泡体物理机械性能的影响,并用体视显微镜表征了泡孔结构。结果表明,随着硫黄用量的增加,再生胶发泡体的密度增大,发泡率、收缩率、泡孔体积分数及泡孔直径均减小,邵尔C硬度和压缩强度增大;随着CZ用量的增加,再生胶发泡体的密度和泡孔直径减小,发泡率和泡孔体积分数先减小后增大,收缩率先增大后减小,压缩强度和邵尔C硬度均先减小后增大;随着TMTD用量的增加,再生胶发泡体的密度增大,发泡率和泡孔体积分数均减小,收缩率和泡孔直径先增大后减小,压缩强度增大后略有下降。