An extrusion die with rollers for foaming polymers

Operation of a flat slot die with rollers for the extrusion foaming of polymers, which has been originally designed by Benkreira et al. (Int. Polym. Proc., 19, 111 (2004)), is considered. The rotation of rollers makes it possible to independently control shear rate inside the die, in the bubble nucleation zone, thus influencing the cell density. In experimental studies of low‐density polyethylene foaming, the influence of the roller rotation speed on the cell density at variable isobutane and talc concentrations and die outlet area has been determined. Based on the fluctuational nucleation theory, a simple model is proposed for estimating the number density of supercritical nuclei formed at the nucleation stage and evaluating the cell density in the foam with allowance for bubble coalescence effects. POLYM. ENG. SCI., 54:96–109, 2014. © 2013 Society of Plastics Engineers     

Multiplex shear stress‐induced nucleation in dynamic microcellular foaming process

The effect of multiplex shear stress on the cell nucleation during microcellular foaming process was investigated using a dynamic foaming experimental apparatus. The multiplex oscillatory shear, which is different from previous one‐dimensional screw shear in a “stable” extrusion foaming process, is applied to the polymer melt through an axially vibrated rotor. The experimental results show that, by superimposing an axial vibration on the rotating rotor, the cell density increases and cell size decreases significantly when the shear rate is low. Both the uniformity of cell size and cell distribution are improved under vibration when compared with that without vibration regardless of how the shear rate changes. In addition, a simplified nucleation model based on shear energy has been carried out to qualitatively investigate the effect of both the simple steady shear and the multiplex oscillatory shear on the cell nucleation. Experiments and theoretical predictions all show that cell nucleation could be greatly improved by superimposing the oscillatory shear when the nucleation driving force induced by the steady shear is insufficient. Finally, the shear heat generated by excessive shear and strong vibration should be considered carefully although the isothermal condition was supposed in the present model. POLYM. ENG. SCI. 46:1728–1738, 2006. © 2006 Society of Plastics Engineers.     

热固性聚氨酯泡沫成核机理的研究

用自制的一套在线显微观测系统研究了热固性聚氨酯泡沫合成初期的气泡成核机理,探讨了聚氨酯发泡过程中搅拌速率(剪切力)、固体成核剂及反应前体系中溶解的气体量等工艺参数对气泡成核过程的影响。通过研究发现,热固性聚氨酯泡沫的成核机理为空气分散成核,在反应原料中添加固体成核剂、增加反应前体系中溶解的气体量以及提高物料的搅拌速率等都可以在一定程度上促进成核。     

振动力场对含有成核剂的微孔塑料泡孔结构的影响

在微孔塑料成型加工过程中,成核剂的加入可以增加泡孔成核点数量,从而增加泡孔密度,改善泡孔的结构,但如果纳米级成核剂在发泡过程中分散性不好,会使泡孔分布不均匀,影响泡孔质量。在实验中,对含有成核剂(纳米碳酸钙)的发泡材料(聚苯乙烯)施加振动场,通过比较发现,施加振动后,纳米级成核剂的分散效果明显改善,颗粒分布变得更均匀,从而使得泡孔分布更均匀,改善了泡孔的结构,提高了微孔塑料泡孔结构质量。     

Flow-induced crystallization from solution: The relative effects of extension and shearing flow fields

Calculations have been performed to evaluate the relative effects of extensional and shearing flow fields on both the chain elongation and crystal nucleation rate enhancement for polyethylene crystallizing from xylene solutions. Rheological behavior was evaluated by means of the elastic dumbbell model modified for nonlinear effects at high elongations, and nucleation rate effects were considered from an essentially phenomenological view point. Molecular weight effects were also incorporated explicitly in the computations. Results show that chain elongation and nucleation rate enhancement is far greater for extensional than for shearing flows. Semiquantitative comparisons with experimental results reported in the literature for various aspects of the flow induced process, including the important fractionation effects, are discussed. Modification of the dumbbell model to account for shear rate effects on the intrinsic viscosity is also discussed.     

挤出发泡片材褶皱分析及模拟计算

结合气泡成核和生长理论模拟分析挤出发泡片材的褶皱生成过程,采用制品出机头口模后单位宽度的增长速率来反映制品褶皱数量,并通过聚苯乙烯挤出发泡实验验证其准确性。结果表明,实验中制品褶皱数量随口模间隙的减小呈先增多后减少的趋势,与模拟计算结果一致;随零切黏度和松弛时间的增大,制品的褶皱数量减少。     

Foam granulation: Binder dispersion and nucleation in mixer-granulators

Traditional wet granulation method involves spraying of liquid binder onto a moving powder bed to granulate the powder particles in the granulator. A new alternative method of wet granulation has been developed where foam delivery of binder is used to granulate the powder particles.This study investigated binder distribution in wet granulation and focused on the nucleation stage, where nuclei are formed during the initial binder distribution. Nucleation experiments were used to study the formation of nuclei by the foam and spray delivery methods in a high shear mixer-granulator. The distribution of foams on a dynamic powder bed were also investigated by filming small portion of foams as they penetrated into moving powder beds under different powder flow conditions in a high shear mixer-granulator.Nucleation experiments in this study show that foam delivery tends to create a narrower nuclei size distribution during the early stage of wet granulation process compared to spray delivery at the same processing conditions, demonstrating the potential of foam granulation in achieving improved binder distribution. For foam delivery, the nuclei formation is influenced by the foam properties and powder flow conditions in the granulator. The experiments show that the narrowest nuclei size distribution is obtained by granulating with high-quality foam and intensive powder mixing conditions. Coarser nuclei are formed when low-quality foam is dispersed in a less intensively agitated powder. The interactions of foam quality and the powder flow pattern are discussed and two distinct wetting and nucleation mechanisms are proposed: (1) under bumping flow, a low-quality foam tends to induce localised wetting and nucleation. The wetting and nucleation is “foam drainage” controlled. (2) Under roping flow, foam will be dispersed by the motion of the agitated powder. The wetting and nucleation is “mechanical dispersion” controlled.     

泡沫塑料加工过程中的气泡成核理论(Ⅱ)——剪切能成核理论及其发展

介绍了剪切流场中泡沫塑料加工的气泡成核理论,分析评述了剪切流场中泡核拉伸模型、空穴成核模型对气泡成核机理的解释及存在的不足;对静态熔体中气泡成核过程进行了能量描述;介绍了最新的气泡成核中的剪切能成核理论,该理论较完善地解释了剪切流场中气泡成核过程;最后指出了气泡成核理论研究的发展方向。     

湿工况下泡沫金属内换热和压降的数值模拟和实验验证

泡沫金属应用到换热器空气侧有望提高析湿工况下的换热性能。为了了解湿空气在泡沫金属内的热质传递和压降特性,建立了泡沫金属内液滴形成、生长和运动特性的数值模型。基于液滴成核数目和成核临界半径得出液滴形成过程的传质率模型;通过建立液滴与湿空气相界面附近湿空气中水蒸气的组分守恒方程,得出液滴生长过程的传质率模型;通过对不同孔棱柱表面液滴的受力分析,建立在重力和风力的共同作用下的液滴接触角模型。将液滴形成及生长的传质率模型和接触角模型分别作为质量源项和表面张力源项,加入连续性方程、动量方程和能量方程组中,实现对泡沫金属内液滴生长、形成和运动过程模拟。模型的实验验证结果表明,换热量预测值与实验结果的最大偏差为11.9%,压降预测值与实验结果的最大偏差为17.7%。     

The effect of processing parameters on cell structure and mechanical properties of extrusion‐foamed poly(vinyl chloride) sheets

The objective of this study was to investigate the effect of processing parameters on cell structure and mechanical properties of extrusion‐foamed poly(vinyl chloride) sheets. For this purpose, the effects of screw speed and die temperature on cell morphology, density, and mechanical properties, including tensile strength, elongation at break, flexural strength, and notched impact strength of the foam samples, were determined under the same conditions. The experimental results indicated that the extrusion‐foaming process was comparatively stable as the screw speed changed in the range of 5.5–8.5 rpm. It was also shown that the lower the die temperature, the higher the die pressure and pressure drop rate, which is conducive to uniform bubble nucleation. In addition, the lower die temperature was beneficial for bubble solidifying and shaping. Therefore, in the range of temperature allowed, the lower the die temperature, the foamed poly(vinyl chloride) sheets with better cell structure and mechanical performance can be obtained. J. VINYL ADDIT. TECHNOL., 22:377–383, 2016. © 2014 Society of Plastics Engineers     

Effect of die geometry on foaming behaviors of high‐melt‐strength polypropylene with CO2

This article reports on a systematic study that was conducted to investigate the effects of die geometry (i.e., pressure and pressure drop rate) on the cell nucleation and growth behaviors of noncrosslinked high‐melt‐strength (HMS) polypropylene (PP) foams blown with supercritical CO₂. The experimental results showed that the cellular morphologies of PP foams were sensitive to the die geometry. Furthermore, the initial expansion behavior of the foam extrudate at the die exit was recorded using a high‐speed CCD camera. This enabled us to achieve a more thorough understanding of the effect of die geometry on both the initial expansion behavior and the final cellular morphology of HMS PP foams. The effect of die temperature on cell morphology was also studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

热塑挤出制备无机阻燃聚乙烯醇泡沫材料及其影响因素的研究

以水为增塑剂兼物理发泡剂,氢氧化铝(ATH)为无机阻燃剂兼异相成核剂,通过热塑挤出方法制备了无机阻燃聚乙烯醇/氢氧化铝(PVAL/ATH)复合泡沫材料,采用扫描电子显微镜(SEM)等研究了水和ATH含量、口模温度、螺杆转速、交联剂对复合泡沫材料泡孔结构的影响。结果表明,适当的口模温度和螺杆转速是实现体系中水的可控、连续、稳定发泡的关键因素,适量添加的阻燃剂能够起到良好异相成核剂的作用,在最佳工艺条件下,当PVAL/ATH/水为100/80/30,口模温度为125℃,螺杆转速为30 r/min时,制备得到综合性能优异的无机阻燃PVAL/ATH泡沫材料,泡沫材料的表观密度为0.32 g/cm3,膨胀倍率为10.0,泡孔密度约为1.6×105个/cm3。此外,引入硼酸作为交联剂,有效提高了熔体强度并改善了泡孔结构,交联后泡沫材料的拉伸强度和断裂伸长率分别提高到6.3 MPa和59.2%。     

Modeling of three‐dimensional flow and heat transfer in polystyrene foam extrusion dies

A three‐dimensional mathematical model was developed to investigate the nonisothermal, non‐Newtonian polymer flow through the dies used in the polystyrene foam extrusion process. The model, based on the computational fluid dynamics (CFD) code, Polyflow, allowed for the shear rate and temperature dependence of the shear viscosity of the blowing agent laden polystyrene melt. The model also accounted for viscous heating. The shear viscosity of the polystyrene‐blowing agent mixture was measured experimentally at several temperatures. The model was used to calculate pressure, flow, and temperature distributions in two different dies used for industrial‐scale extrusion of polystyrene foams. The article presents a selection of computed results to illustrate the effect of die design on uniformity of flow at the die exit, the overall pressure drop in the die, relative magnitudes of pressure drop in the land section versus the rest of the die, and temperature distribution in the die. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Rheological aspects of thermoplastic foam extrusion

Several rheological aspects of thermoplastic foam extrusion are described by a phenomenological model of the flow in an extrusion die. The macroscopic effects of the phase change, from a homogeneous polymer melt that contains a blowing agent, to a foam, are described in terms of two dimensionless parameters. α is defined as the ratio of the pressure gradient in the melt phase to the average pressure gradient in the foam phase. Θ represents the ratio of the pressure drop in the melt phase to the pressure drop in the foam phase. The position at which the phase change initiates, the exit contribution to the Bagley ends pressure correction, and the true wall shear stress in the melt phase are related to α and Θ. The quality of the foam produced is discussed in terms of the extrusion conditions and their effect on the foaming position in the die. It is demonstrated that the ends pressure correction cannot be neglected on the basis of a long die alone. Asymptotic conditions for which the phase change has negligible effect on the melt flow rate are predicted. α is calculated from the data of Han and Villamizar, who measured the pressure distribution in the die and observed the phase change directly. The prediction of α from theory is complicated by the lack of suitable constitutive relations for the foam phase. Since Θ only requires knowledge of the pressure at which the phase change initiates, it is relatively easy to evaluate.     

动态发泡工艺参数对PS微孔塑料泡孔结构的影响

以超临界CO2为发泡剂,用振动诱导发泡模拟装置研究了微孔塑料动态成型过程中气体饱和压力、压力释放速率、温度、气体饱和时间、稳态剪切速率、振动等工艺参数对聚苯乙烯（PS）微孔塑料泡孔结构的影响。研究发现,PS微孔塑料试样的泡孔结构随着气体饱和压力和压力释放速率的提高而得到改善,而温度、气体饱和时间、稳态剪切速率则存在一个最佳的操作范围,在此范围内制得的PS微孔塑料试样泡孔密度最大,泡孔尺寸最小。在稳态剪切速率一定的情况下,通过施加振动可以进一步改善泡孔结构．     

剪切流场中气泡成核理论的研究

针对经典成核理论在描述流场中气泡成核行为时的局限性，根据缝模流道中的剪切成核实验结果，提出了剪切流场下描述气泡成核的剪切能成核理论，并与文献中其它剪切促进气泡成核的解释进行了比较，从而进一步完善了剪切流场中的气泡成核理论。     

Modeling flow and cell formation in foam sheet extrusion of polystyrene with CO2 and co-blowing agents. Part II: Process model

In foam extrusion, process parameters, material properties, and the blowing agent have an influence on the resulting foam properties. For safety and environmental reasons, carbon dioxide (CO₂) has gained importance as physical blowing agent for the production of low-density polystyrene foam sheets. The sole use of CO₂ often leads to corrugation, open cell structures, or surface defects on the foam sheet. As an alternative, blowing agent mixtures based on CO₂ and organic solvents such as ethanol, acetone, or ethyl acetate can be used, changing solubility and flow behavior of the gas-loaded melt. A model approach for describing foam extrusion of polystyrene with various blowing agent mixtures in an annular gap die is developed. Part I of the paper describes the modeling of material properties. In Part II, the process model including nucleation and cell formation in the flow field is developed and applied to a foam sheet extrusion process. Based on the material model, melt flow and formation of cells are modeled by a step-wise calculation along the die, showing good agreement with experimental data. Dimensionless numbers are used to describe the foaming process and a parameter study based on these dimensionless numbers is presented.     

剪切流场中聚乙烯结晶过程的建模与模拟

基于Eder模型推导了剪切流场中球晶、串晶形态演化的数学模型,将第一法向应力差作为串晶成核的驱动,并引入两相悬浮模型描述体系,认为其由无定形相和半结晶相组成,分别用FENE-P模型和刚性哑铃模型描述。基于上述数学模型,分别构造了捕捉球晶、串晶生长的Monte Carlo法与体系控制方程求解的有限差分法,成功模拟了二维剪切流场中聚乙烯的结晶过程,给出了球晶、串晶的形态演化,分析了剪切时间、剪切速率对串晶成核密度、结晶速率、流体黏度等的影响。数值结果表明:所构造的Monte Carlo法合理有效,不仅成功捕捉了晶体的生长与碰撞,而且较为准确地预测了结晶速率。此外,提高剪切时间或剪切速率,将增加串晶成核密度、提高结晶速率、使流体黏度突增的时间点提前。     

Direct preparation of battery-grade lithium carbonate via a nucleation–crystallization isolating process intensified by a micro-liquid film reactor

With the lithium-ion battery industry booming, the demand for battery-grade lithium carbonate is sharply increasing. However, it is difficult to simultaneously meet the requirements for the particle size and the purity of battery-grade lithium carbonate. Herein, the nucleation–crystallization isolating process (NCIP) is applied to prepare battery-grade lithium carbonate without any post-treatment procedure. The nucleation process is intensified by a micro-liquid film reactor (MLFR), where the feedstock solution is subject to intensive shear force and centrifugal force. The feedstock solutions are mixed rapidly and a large number of nuclei form instantly in the MLFR. After nucleation, the crystallization process is achieved in another reactor. A few new nuclei form in the crystallization process. The nucleation intensification in the MLFR is verified by computational fluid dynamics (CFD) simulations and experimental results. The particle size distribution is narrower and the impurity residue in the products is far lower than that prepared by a traditional precipitation method. The effects of nucleation and crystallization on the particle size distribution and purity were investigated. In the optimized operation parameters, the particle size distribution of the Li₂CO₃ product is D₁₀ = 2.856 μm, D₅₀ = 5.976 μm, and D₉₀ = 11.197 μm, and the purity is 99.73%, both of which meet the requirements of battery-grade Li₂CO₃. Moreover, the lithium recovery rate is increased to 88.21% compared to that prepared by a traditional precipitation method (79.0%). This work provides an alternative way for the preparation of high-purity chemicals by process intensification.     

Foam extrusion characteristics of thermoplastic resin with fluorocarbon blowing agent. II. Polystyrene foam extrusion

The foam extrusion characteristics of three different grades of polystyrene resin were investigated. For the study, cylindrical dies with various values of length-to-diameter ratio, entrance angle, and reservior-to-capillary diameter ratio were used. Fluorocarbon blowing agents were used, and mixtures of citric acid and sodium bicarbonate were used as nucleating agent. It was found that the die temperature, shear rate, the type and concentration of blowing agent, and die geometry affect the quality of the extruded polystyrene foam. Foam density and open cell fraction were used in determining the quality of extruded foams. We have found that the extrudate swell ratio is correlatable to foam density, independent of the die temperature employed. However, the die temperature has been found to be a very sensitive processing variable governing the quality of extruded foams.