Effect of the pressure drop rate on cell nucleation in continuous processing of microcellular polymers

Microllular plastics are cellular polymers characterized by cell densities greater than 10⁹ cells/cm³ and cells smaller than 10 μm. One of the critical steps in the continuous production of microcellular plastics is the promotion of high cell nucleation rates in a flowing polymer matrix. These high nucleation rates can be achieved by first forming a polymer/gas solution followed by rapidly decreasing the solubility of gas in the polymer. Since, in the processing range of interest, the gas solubility in the polymer decreases as the pressure decreases, a rapid pressure drop element, consisting of a nozzle, has been employed as a continuous microcellular nucleation device. In this paper, the effects of the pressure drop rate on the nucleation of cells and the cell density are discussed. The experimental results indicate that both the magnitude and the cell density are discussed. The experimental results indicate that both the magnitude and the rate of pressure drop play a strong role in microcellular processing. The pressure phenomenon affects the thermodynamic instability induced in the polymer/gas solution and the competition between cell nucleation and growth.     

Effect of dissolved gas on the viscosity of HIPS in the manufacture of microcellular plastics

The microcellular plastics (MCPs) process is a foaming process that has been developed to reduce the weight of a product without significant changes to the mechanical properties. To apply microcellular plastics to mass production systems such as extrusion, injection molding, and blow molding, research must be done on material properties, such as viscosity, glass transition temperature, and melt index of polymer resin. Among the properties, it is critical to predict the change in viscosity with the amount of inert gas, which can be an index of the injection molding working condition of polymer resin. The purpose of this paper is to study the relationship between the amount of dissolved gas and the viscosity of high impact polystyrene (HIPS) resin in extrusion. The experiment was carried out with newly designed gas supply equipment and with a screw and die modified for MCPs. In addition, a pressure gauge was set up on the end of a barrel for measuring the pressure change. The experiment has shown that the viscosity of polymer decreases with increasing amounts of inert gas. A new model was applied to estimate the viscosity change as a function of the amount of dissolved gas.     

An extrusion system for the processing of microcellular polymer sheets: Shaping and cell growth control

A new processing system for the extrusion of microcellular polymer sheets is presented. Specifically, the detailed design of a shaping and cell growth control system is discussed in the context of an overall extrusion system design with particular emphasis on the system level functional requirements of cell nucleation, cell growth, and shaping. The principle of the basic extrusion system design is to shape a nucleated polymer/gas solution flow under pressure and accurate temperature control. In this way, the initial cell growth is controlled so as to prevent degradation of the nucleated cell density during shaping. Two foaming die designs for satisfying the initial shaping and cell growth requirements are presented. Critical experiments are then presented which verified the concept of shaping a nucleated polymer/gas solution. Moreover, these experiments demonstrated the feasibility of the overall microcellular polymer sheet extrusion system design.     

Microcellular sheet extrusion system process design models for shaping and cell growth control

The feasibility of shaping a nucleated polymer/gas solution represents a significant advancement for microcellular plastics process technology. Through proper design of the foaming die, nucleated solution flows can be shaped to arbitary dimensions while maintaining the functional independence of cell nucleation, cell growth and shaping. To maintain funcational independence, stringent pressure and temperature design specifications, which supersede those of conventional foam processing, must be met by the foaming die design. As a means of aiding the design process, a model is developed for predicting pressure losses and flow rates of nucleated polymer/gas solutions. A comparison of the model predictions and the actual foaming die design performance shows good agreement for limited data. These relatively simple models capture the major physics of the complicated two-phase flow field and provide a sound base from which scale-up of the foaming die concept can be achieved. The nucleated polymer/gas solution flow models predict highly nonlinear volumetric flow rates contrasting constant flow rates predicted for the neat polymer flow. In addition, a convenient method for classifying nucleated polymer/gas solution flow is presented based on a dimensionless ratio of the characteristic flow rate to the characteristic gas diffusion rate.     

Microcellular extrusion of PLA utilizing solid‐state nucleation in the gas‐saturated pellet extrusion process

In this study, we explore the use of solid‐state nucleation in polymer pellets as a means to create microcellular PLA foams in extrusion. This is achieved by using gas‐saturated PLA pellets as input to the extruder. Foam density, bubble size, and bubble density is reported and compared with microcellular foams created in the gas‐injection extrusion process. PLA pellet gas concentrations between 17 and 29 mg CO₂/g PLA was found to produce quality microcellular foams in this process. Gas concentrations within this range were achieved by varying methods that included partial saturation, desorption from full saturation, and blending saturated with unsaturated pellets. This gas concentration window that produced microcellular foams was found to be independent of the saturation and desorption process used to achieve the desired concentration. We further compare the pressure drop and pressure drop rate of the gas‐saturated pellet extrusion process showing that similar foams can be produced at pressures orders of magnitude lower than the alternative gas‐injection extrusion processes. Investigations into extrusion pressures support the hypothesis that the gas‐saturated pellet extrusion process utilizes solid‐state nucleation in the feed section of the extruder to achieve high bubble density foams. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Change in the critical nucleation radius and its impact on cell stability during polymeric foaming processes

The critical radius of cell nucleation is a function of the thermodynamic state that is uniquely determined by the system temperature, system pressure, and the dissolved gas concentration in the polymer/gas solution. Because these state variables change continuously during the foaming process, the critical radius varies simultaneously despite the traditional concept that it is a fixed thermodynamic property for a given initial state. According to classical nucleation theory, the critical radius determines the fate of the bubbles. Therefore, the change in the critical radius during foaming has a strong impact on the stability of foamed cells, especially in the production of microcellular or nanocellular foams. In this study, the continuous change in the critical radius is theoretically demonstrated under atmospheric pressure while bubbles are generated and expanded by the decomposition of a chemical blowing agent. The experimental results observed from the visualization cell are used to support the theoretically derived concept. Sustainability of the nucleated bubbles is also discussed by comparing the bubble size to the critical radius.     

Steady flow simulation of a polymer‐diluent solution through an abrupt axisymmetric contraction using internally consistent rheological scaling

In this work, a new methodology is developed that describes the viscoelastic scaling of a polymer‐physical foaming agent (PFA) solution in a detailed and internally consistent manner. The approach is new in that while previous researchers have largely focused on scaling down experimentally obtained high pressure polymer‐PFA solution viscosity data onto a master curve for the viscosity of the undiluted polymer melt at a reference temperature and atmospheric pressure, we have generated the shear viscosity data required for our simulations by systematically scaling up the viscosity values obtained from measurements on a pure polymer melt to the desired temperature, pressure, and concentration values characterizing the flow. Simulations have been run for the flow of a polymer‐PFA solution through an extrusion foaming die with an abrupt axisymmetric contraction and good qualitative agreement is obtained with experimental pressure drop measurements obtained previously in our laboratory. The pressure drop rates and temperature rise rates have been estimated at the surface of incipient nucleation. Because of the short residence times in the die for the microcellular foaming process, approximating the flow through the die as a single phase flow in our simulations still gives useful insights into the dynamics of the flow. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

聚合物/超临界CO2挤出发泡中影响进气状况的因素

研究了聚合物／超临界CO2挤出发泡中影响进气状况的因素，实验显示，挤出机压力分布应保证CO2在挤出全程都处于超临界条件下；进气点应设在熔融段与计量段之间，以保证聚合物熔化和进气后气体与聚合物的混合；进气压力与熔体压力之差越大，则进气量越大，合理的压力差为5～8MPa；进气量的大小主要受溶解度影响．可用压力差控制。     

超临界CO2在聚苯乙烯熔体中的扩散系数

微孔发泡材料的质量与超临界CO2在聚合物熔体中的溶解量和溶解速率紧密相关,采用有限元模拟的方法得出不同条件下的等效扩散系数来表征溶解速率.首先,通过基于体积法的实验装置测出不同条件下超临界CO2在聚合物熔体中的溶解量;其次,通过COMSOL软件计算得出不同的扩散系数下溶解量的变化,最后通过实验值与模拟计算值之间的对比,...     

Microcellular foaming of polypropylene containing low glass transition rubber particles in an injection molding process

Microcellular foams in polypropylene containing rubber particles were produced in an injection molding process. The foams are generated because of the thermodynamic instability and are controlled by formation process. The effect of processing parameters on microcellular foaming was investigated in the injection molding process. Injection speed and pressure are less important factors but packing pressure plays an important role in controlling the foam density. A critical packing pressure, about 5 × 10⁶ Pa, was found to generate microcellular foams in our polypropylene material system. Rubber particles inside the polypropylene seem to stabilize the microcellular foams.     

开孔型聚合物微发泡材料研究进展

通过回顾目前几种微孔材料成型的主要方法,介绍了微发泡成型技术用于制备开孔型微孔材料的必要性。讨论了关于开孔型聚合物微发泡材料制备技术及研究方法的几种思路,分别是不相容聚合物共混、泡孔合并模型、熔融挤出发泡、开孔剂法和气体浓度阈(值)等方法,这些方法的微孔成型机理各不相同,所制备的材料微观结构也各有特点。文献分析表明:微发泡成型方法用于开孔型微孔材料的制备是一种非常有前景的技术。     

微孔发泡过程中聚合物/超临界CO2均相体系形成的研究

阐述以超临界CO2为发泡剂的微孔发泡中均相体系的形成过程，研究聚合物熔体和气体的混合机理，并分析影响均相体系形成过程的因素。结果表明，聚合物和气体本身的结构和性质、工艺条件、加工设备、外力场等均影响均相体系的形成，振动力场的引入可以提高多相体系的混合程度，在聚合物／气体均相体系的形成过程中引入振动力场是一个全新的研究方向。     

聚合物纳米复合材料微孔发泡及其影响因素的研究概况

结合聚合物异相成核的空穴模型,分析了含添加剂的聚合物异相成核理论。纳米级添加剂粒子比微米级添加剂粒子具有更小的尺寸和更大的表面积,与聚合物基体的接触更加紧密,因此其发泡制品具有更好的泡孔结构和性能。分析了聚合物/粘土纳米复合材料用超临界CO2发泡过程的影响因素。结果表明,剥离型纳米复合材料具有更小的泡孔尺寸和更大的泡孔密度。聚合物纳米复合材料与连续挤出发泡过程的结合为微孔发泡提供了一项新的技术。     

Effect of die temperature on the morphology of microcellular foams

A study on the extrusion of microcellular polystyrene foams at different foaming temperatures was carried out using CO₂ as the foaming agent. The contraction flow in the extrusion die was simulated with FLUENT computational fluid dynamics code at two temperatures (150°C and 175°C) to predict pressure and temperature profiles in the die. The location of nucleation onset was determined based on the pressure profile and equilibrium solubility. The relative importance of pressure and temperature in determining the nucleation rate was compared using calculations based on classical homogeneous nucleation theory. Experimentally, the effects of die temperature (i.e., the foaming temperature) on the pressure profile in the die, cell size, cell density, and cell morphology were investigated at different screw rotation speeds (10 ～ 30 rpm). Experimental results were compared with simulations to gain insight into the foaming process. Although the foaming temperature was found to be less significant than the pressure drop or the pressure drop rate in deciding the cell size and cell density, it affects the cell morphology dramatically. Open and closed cell structures can be generated by changing the foaming temperature. Microcellular foams of PS (with cell sizes smaller than 10 μm and cell densities greater than 10 cells/cm³) are created experimentally when the die temperature is 160°C, the pressure drop through the die is greater than 16 MPa, and the pressure drop rate is higher than 10⁹ Pa/sec.     

A microcellular processing study of poly(ethylene terephthalate) in the amorphous and semicrystalline states. Part I: Microcell nucleation

Microcellular semicrystalline polymers such as poly(ethylene terephthalate) show great promise for engineering applications because of their unique properties, particularly at higher densities. Recent studies reveal some high density microcellular polymers have longer fatigue lives and/or equal strengths to the neat polymer. Relatively few microcellular processing studies of semicrystalline polymers have been presented. In general, semicrystalline polymers are relatively difficult to microcellular process compared to amorphous polymers. In this paper and a companion paper, the microcellular processing of poly(ethylene terephthalate) in the amorphous and semicrystalline states is studied in order to quantify the processing differences. The microcellular processing steps addressed in this paper include gas/polymer solution formation and microvoid nucleation. Particular emphasis is given to microvoid nucleation comparing the processing characteristics of semicrystalline and amorphous materials. Moreover, this study identifies a number of critical process parameters. In general, the semicrystalline materials exhibit ten to one thousand times higher cell nucleation densities compared with the amorphous materials, resulting from heterogeneous nucleation contributions. The amorphous materials show a strong dependence on cell density, while the semicrystalline materials show a weaker dependence. Moreover, classical nucleation theory is not adequate to quantitatively predict the effects of saturation pressure on cell nucleation for either the amorphous or semicrystalline polyesters. Both the semicrystalline and amorphous materials exhibit constant nucleation cell densities with increasing foaming time. Foaming temperatures near the glass transition are found to influence the cell density of the amorphous polyesters, indicating some degree of thermally activated nucleation. Furthermore, classical nucleation theory is not adequate to predict the cell density dependence on foaming temperature. Similar to the amorphous polyesters above the glass transition temperature, nucleation in the semicrystalline materials is found to be independent of the foaming temperature.     

Continuous extrusion of microcellular polycarbonate

Extruded microcellular foams have been obtained from mixtures of polycarbonate (PC) and n‐pentane. Cell diameters were in the range of 2 to 5 μm and the foam densities varied between 400 and 700 kg/m³. Although two types of PC have been investigated, one linear and one branched, the presence of side branchings did not modify the extruded foam characteristics. Use of carbon dioxide as the blowing agent was also attempted, and cell sizes below 10 μm have been successfully obtained. One prerequisite for microcellular foaming was believed to consist in a concentration of the blowing agent close to its limit of solubility as that defined under the actual processing conditions of pressure and temperature. This hypothesis was validated from the observation of extrusion of regular PC foams (intermediate to low densities and cell sizes ranging between 100 μm and 1 mm) using moderate concentrations of blowing agents, and from solubility and viscosity measurements on similar polymer/blowing agent systems.     

Polystyrene microcellular plastic generation by quick‐heating process at high temperature

Generation of microcellular plastic in the polystyrene‐nitrogen system was studied in a batch process. In this study, a quick‐heating method was applied to study the effects of saturation temperature, decompression rate and heating time on the microcellular structure for sheet samples with a thickness of 1.3 mm. The saturation pressure in each process was kept constant at 25 MPa. At saturation temperatures above 393 K, we found that, although the solubility of nitrogen increased with increasing saturation temperature, cell density decreased, and the average cell diameter and volume expansion ratio increased. The samples that were saturated at 433 K shattered after microcellular processing. The change in decompression rate affected the supersaturation degree of the dissolved gas in the polymer, and affected the cell structure. Variation of heating time for difference saturation/heating temperature could be used to obtain the optimum relation between cell density, average cell diameter, and volume expansion ratio.     

Open-celled microcellular foaming and the formation of cellular structure by a theoretical pattern in polystyrene

An open-celled structure was produced using polystyrene and supercritical carbon dioxide in a novel batch process. The required processing conditions to achieve open-celled structures were predicted by a theoretical model and confirmed by the experimental data. The theoretical model predicts that at least a saturation pressure of 130 bar and a foaming time between 9 and 58 s are required for this system to produce an open-celled structure. The foaming temperature range has been selected to be higher than the polymer glass transition temperature yet not higher than a temperature limit where the gas starts leaving the system. The experimental results in the batch foaming process verified the model substantially. The SEM pictures showed the presence of pores between the cells, and the mercury porosimetry test results verified the overall open-celled structure. Experimental results also showed that by increasing the saturation pressure and the foaming temperature, there was a drop in the time required for open-celled structure formation. At saturation pressure of 130 bar, foaming temperature of 150 °C and a foaming time of 60 s, open-celled microcellular polystyrene foams were obtained using supercritical CO₂ in the batch process. Based on the results, a schematic diagram, depicting the process of foam structure formation from nucleation to bubble coalescence and gas escape from polymer, was proposed. Theoretical calculations showed that by increasing foaming time, cell size was increased and cell density was reduced and the experimental results verified this prediction.     

Preparation of microcellular poly(ethylene‐co‐octene) rubber foam with supercritical carbon dioxide

In the past 3 decades, there has been great advancement in the preparation of microcellular thermoplastic polymer foams. However, little attention has been paid to thermoplastic elastomers. In this study, microcellular poly(ethylene‐co‐octene) (PEOc) rubber foams with a cell density of 2.9 × 10¹⁰ cells/cm³ and a cell size of 1.9 μm were successfully prepared with carbon dioxide as the physical blowing agent with a batch foaming process. The microcellular PEOc foams exhibited a well‐defined, closed‐cell structure, a uniform cell size distribution, and the formation of unfoamed skin at low foaming temperatures. Their difference from thermoplastic foam was from obvious volume recovery in the atmosphere because of the elasticity of the polymer matrix. We investigated the effect of the molecular weight on the cell growth process by changing the foaming conditions, and two important effect factors on the cell growth, that is, the polymer matrix modulus/melt viscoelastic properties and gas diffusion coefficient, were assessed. With increasing molecular weight, the matrix modulus and melt viscosity tended to increase, whereas the gas solubility and diffusion coefficient decreased. The increase in the matrix modulus and melt viscosity tended to decrease the cell size and stabilize the cell structure at high foaming temperatures, whereas the increase in the gas diffusion coefficient facilitated cell growth at the beginning and limited cell growth because most of the gas diffused out of the polymer matrix during the long foaming times or at high foaming temperatures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

PVC微孔塑料的研究进展

阐述化学发泡剂、物理发泡剂和添加剂对PVC微孔发泡的影响,综述了PVC微孔发泡成型方法的研究进展,包括间歇成型法、连续挤出成型法和电磁动态挤出成型法。将振动力场引入到微孔发泡过程为PVC微孔塑料连续挤出成型提供了新的思路和研究方向。