Morphological analysis of microcellular PP produced in a core‐back injection process using chemical blowing agents and gas counter pressure

A complete experimental analysis of the microcellular injection process using Chemical Blowing Agents (CBA) with Gas Counter Pressure (GCP) and core‐back expansion is presented. Three different types of polypropylene, neat and charged, were mixed with two different CBAs and injected into a plate mold with varying process parameters. First, an exhaustive cartographical mapping of the plate morphology is analyzed. In a second step, the relation between injection parameters and the resulting morphology is investigated. The results show that injection time affects the cellular structure. The formulation, especially the type of chemical foaming agent, controls the average bubble radius. Compared with classical injection process, the use of CBAs, combined to Gas Counter Pressure and core‐back process, allows obtaining parts with good surface aspect, more homogeneous cellular structures and smaller bubble radius. POLYM. ENG. SCI., 55:2465–2473, 2015. © 2015 Society of Plastics Engineers     

The importance of timely polymer sintering while processing polypropylene foams in rotational molding

Producing polypropylene (PP) foams with satisfactory cell morphologies in rotational foam molding is feasible. However, the narrow interval between the melting temperature of PP and the onset decomposition temperature of the applicable chemical blowing agent (CBA), and the relatively low melt strength of PP at elevated temperatures are considered the greatest obstacles in processing PP foams. The experimental results revealed that the morphology of the foams obtained by processing PP pellets that have been pre‐compounded with a CBA could be governed by either pellet sintering or cell coalescence. The viscosity of the basic PP resin and the processing temperature determine which of these two key factors will assume a predominating influence towards the foaming process. The desired volume expansion ratio (VER) of the foam also plays an important role since it determines the formulation of the foamable resin and the shot size. Desirable PP foam structures in compounding based rotational foam molding can be obtained only if pellet sintering takes place prior to the decomposition of the CBA and if the processing temperature during the foaming process is kept lower than the temperature of cell coalescence.     

Batch foaming of SAN/clay nanocomposites with scCO2: A very tunable way of controlling the cellular morphology

This paper aims at elucidating some important parameters affecting the cellular morphology of poly(styrene-co-acrylonitrile) (SAN)/clay nanocomposite foams prepared with the supercritical CO₂ technology. Prior to foaming experiments, the SAN/CO₂ system has first been studied. The effect of nanoclay on CO₂ sorption/desorption rate into/from SAN is assessed with a gravimetric method. Ideal saturation conditions are then deduced in view of the foaming process. Nanocomposites foaming has first been performed with the one-step foaming process, also called depressurization foaming. Foams with different cellular morphology have been obtained depending on nanoclay dispersion level and foaming conditions. While foaming at low temperature (40 °C) leads to foams with the highest cell density (∼10¹²-10¹⁴ cells/cm³), the foam expansion is restricted (d∼0.7-0.8 g/cm³). This drawback has been overcome with the use of the two-step foaming process, also called solid-state foaming, where foam expansion occurs during sample dipping in a hot oil bath (d∼0.1-0.5 g/cm³). Different foaming parameters have been varied, and some schemes have been drawn to summarize the characteristics of the foams prepared - cell size, cell density, foam density - depending on both the foaming conditions and nanoclay addition. This result thus illustrates the huge flexibility of the supercritical CO₂ batch foaming process for tuning the foam cellular morphology.     

Foaming behavior of high‐melt strength polypropylene/clay nanocomposites

The foaming behavior of high‐melt strength polypropylene (HMS‐PP) and HMS‐PP/Cloisite 20A nanocomposites (PPNC) was studied in a batch process. PPNCs with 2, 4, 8, and 10 wt% clay were prepared in a twin screw extruder. The morphology of the nanocomposites was studied using XRD and TEM. Subsequently, foaming experiments were conducted using supercritical CO₂ as the blowing agent in a batch process, and foams with cell sizes varying from the sub micrometer to the micro meter range were prepared. The effect of variation in saturation pressure and temperature, foaming temperature, foaming time, and quench temperature was determined experimentally. Dynamic rheological measurements were conducted to relate the influence of nanocomposites morphology with foam cell growth and nucleation. Extensional rheological measurements were also conducted to detect the presence of strain hardening effect at the foaming temperatures used in the experiment. It was found that the nucleation efficiency of clay reduces with increase in clay loading. Also, the optimum amount of filler for generation of fine celled foams was found to be around the percolation threshold of the polymer. The extended strain hardening effect shown by the polymer in presence of clay plays an important role in stabilizing foam cell sizes. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Novel injection molding foaming approaches using gas‐laden pellets with N2, CO2, and N2 + CO2 as the blowing agents

A novel method of producing injection molded parts with a foamed structure has been developed. It has been named supercritical fluid‐laden pellet injection molding foaming technology (SIFT). Compared with conventional microcellular foaming technologies, it lowers equipment costs without sacrificing the production rate, making it a good candidate for mass producing foamed injection molded parts. Both N₂ and CO₂ can be suitably used in this process as the physical blowing agent. However, due to their distinct physical properties, it is necessary to understand the influence of their differences over the process and the outcomes. Comparisons were made in this study between using CO₂ and N₂ as the blowing agents in terms of the part morphologies, as well as the shelf life and gas desorption process of the gas‐laden pellets. After gaining a good understanding of the SIFT process and the gas‐laden pellets, a novel foam injection molding approach combining the SIFT process with microcellular injection molding was proposed in this study. Both N₂ and CO₂ can be introduced into the same foaming process as the coblowing agents in a two‐step manner. Using an optimal content ratio for the blowing agents, as well as the proper sequence of introducing the gases, foamed parts with a much better morphology can be produced by taking advantage of the benefits of both blowing agents. In this study, the theoretical background is discussed and experimental results show that this combined approach leads to significant improvements in foam cell morphology for low density polyethylene, polypropylene, and high impact polystyrene using two different mold geometries. POLYM. ENG. SCI., 54:899–913, 2014. © 2013 Society of Plastics Engineers     

Improvement of the dispersity of micro-nano particles for PP/PVC composites using gas-assisted dispersion in a controlled foaming process

Polyvinyl chloride (PVC) and nanosilicon dioxide (nano-SiO₂) were blended with neat polypropylene (PP) to improve its flame retardancy and cellular foam structure, and the dispersal effects of PVC and nano-SiO₂ and the foaming effect of the PP/PVC composites were investigated. PP/PVC samples with different compositions and foaming degrees were first fabricated by conventional injection molding with and without a blowing agent. Tensile testing, differential scanning calorimetry, scanning electron microscopy, limiting oxygen index testing, and vertical burn testing were used to study the mechanical properties, thermal features, microstructures, and flame-retardant properties of the molded samples, and the samples with different degrees of foaming were compared. The results suggest that the foaming process facilitates the dispersion of PVC and nano-SiO₂, while the presence of PVC and nano-SiO₂ improves the foamability of PP. A method for a gas-assisted dispersion technology to control the foaming process was hence proposed. Considering that the mechanical properties of PP/PVC could be retained with satisfactory flame retardancy and weight loss, convenient processing, and low-cost materials; the technology presented can be directly applied for lightweight engineering and the manufacture of fire-resistant material and can act as a reference for other micro-nano processing involving the dispersion of particles. POLYM. ENG. SCI., 60:524–534, 2020. © 2019 Society of Plastics Engineers     

Investigation of thermoplastic elastomer (TPE) foaming process using blowing agent by rheological and morphological methods

The effects of a chemical blowing agent (CBA) or an encapsulated physical blowing agent (PBA) on morphological development in ethylene octene copolymer (EOC) matrix using dicumyl peroxide (DCP) as a curing agent were investigated by rheological, mechanical, and morphological methods. Temperature ramp tests were carried out to understand curing and foaming processes. Curing temperature (T_cure) was determined as the crossover temperature where storage modulus G′ coincided with loss modulus G′′ in the rheological point of view. For the CBA, T_cure increased with increasing CBA concentration, whereas for the PBA, T_cure decreased with increasing PBA concentration. Other critical temperatures T_1st, T_2nd by foaming process were determined using the axial normal force. With these critical temperatures (T_cure, T_1st, T_2nd), curing and foaming mechanisms can be estimated. Simultaneously, volume expansions of samples were observed with camera. Morphology and mechanical analysis were conducted on fully cured and foamed ECP (is defined as EOC with DCP) with blowing agent. ECP with the CBA exhibited an irregular open-cell structure, whereas when produced using the PBA, it formed a regular closed-cell structure. Specific tensile strength tended to increase with increasing PBA concentration but as blowing agent concentration increased elongation at break decreased. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47358.     

Foaming of polypropylene with supercritical carbon dioxide: An experimental and theoretical study on a new process

A new process was used to foam polypropylene (PP) with batch foaming technique with supercritical carbon dioxide (scCO₂) as the blowing agent. Comparing with the conventional process, the new one takes less time to foam and the foaming temperature range is much broader, which is about 2.5 h and 55°C, respectively. An activation model was established on the basis of mass equilibrium, this model was combined with classical nucleation theory and S‐L EOS model to explain foaming behaviors of PP and simulate the cell nucleation and cell diameter. A satisfactory agreement between calculated and experimental values was obtained. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2877–2885, 2013     

二次开模距离对微发泡聚丙烯材料发泡行为的影响

采用化学发泡注塑成型技术,在二次开模条件下制备微发泡聚丙烯(PP)材料;通过热力学分析法研究了二次开模距离对PP微发泡材料发泡行为的影响。结果表明:二次开模距离能有效地控制PP材料的发泡过程,二次开模距离越小,体系的发泡过程越容易自发进行。当二次开模距离L=5.3 mm时,体系中的吉布斯自由能小于零,发泡过程不可能自发进行;二次开模距离L=4.3 mm时,PP体系的发泡质量最理想,泡孔平均直径为21.6 m,泡孔密度为5.63×106个/cm3,能够获得泡孔细小、均匀的微发泡PP材料。     

Production of non‐crosslinked thermoplastic foams with a controlled density and a wide range of cellular structures

A novel foaming route, with respect to existing industrial foaming processes, called “Improved Compression Molding” (ICM), which allows producing non‐crosslinked thermoplastic foams in a wide density range, is described in this work. This process is different from others because it is possible to control independently density and cellular structure and therefore, tailored cellular polymers can be produced. To understand the process, a collection of polypropylene foams, with relative densities ranging from 0.3 to 0.6 were produced. The influence of foaming parameters, on foams microstructure and mechanical response was analyzed. Results revealed that for similar densities, foams with different open cell content and cell size can be achieved. In addition, it was proved that mechanical behavior strongly depends on the degree of interconnectivity of the cells. The analysis of the relative mechanical properties allowed determining the influence of microstructure on mechanical behavior as well as quantifying the efficiency of the foaming process to produce light‐weight stiff materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42324.     

Visual observation and numerical studies of N2 vs. CO2 foaming behavior in core‐back foam injection molding

We investigated , by visual observation and numerical calculations , the foaming behavior of polypropylene within a foam injection mold cavity with the environmentally benign physical blowing agents nitrogen (N₂) and carbon dioxide (CO₂) . An 85‐ton core‐back injection‐molding machine with temperature and pressure monitoring systems as well as a high‐pressure view cell was used for the investigation . The experiments showed a prominent difference in bubble nucleation and growth between N₂ and CO₂ injection foaming . Even when the weight concentration of N₂ dissolved in polymer was one‐third that of CO₂ , N₂ injection foaming provided a bubble number density that was 30 times larger and a bubble size that was one‐third smaller compared to CO₂ injection foaming . Classical bubble nucleation and growth models developed for batch foaming were employed to analyze these experimental results . The models reasonably explained the differences in injection foaming behavior between N₂ and CO₂ . It was clearly demonstrated by both experiments and numerical calculations that N₂ provides a higher number of bubbles with a smaller bubble size in foam injection molding compared to CO₂ as a result of the lower solubility of N₂ in the polymer and the larger degree of super‐saturation . POLYM. ENG. SCI., 2011. ©2011 Society of Plastics Engineers     

加工参数及配方对PP/LLDPE共混物泡孔形态的影响

采用高压毛细管流变仪对不同含量碳酸钙(CaCO3)的聚丙烯/线型低密度聚乙烯(PP/LLDPE)共混物的流变性能进行了表征;并利用自制的实验装置,在不同发泡温度和饱和压力下,对共混物进行了超临界CO2模拟挤出发泡实验研究。结果表明:使用高熔体强度聚丙(烯HMSPP)发泡可以获得较好的泡孔形态;添加成核剂CaCO3可以使发泡试样的泡孔结构更加规则,泡孔分布更加均匀;随着CaCO3含量的增加,共混物的稠度上升,非牛顿指数降低,当CaCO3含量为3%时,共混物的发泡效果较好;130℃为最佳发泡温度,此时发泡试样的结构完整尺,寸均匀;随着饱和压力的增加发,泡试样的泡孔密度也有所提高。     

Foaming behavior of microcellular foam polypropylene/modified nano calcium carbonate composites

A new process was used to prepare microcellular foams with supercritical carbon dioxide as the physical foaming agent in a batch. The foaming temperature range of the new process was about five times broader than that of the conventional one. Characterization of the cellular structure of the original polypropylene (PP) and PP/nano‐CaCO₃ (nanocomposites) foams was conducted to reveal the effects of the blend composition and processing conditions. The results show that the cellular structure of the PP foams was more sensitive to the foaming temperature and saturation pressure variations than that of the nanocomposite foams. Uniform cells of PP foams are achieved only at a temperature of 154°C. Also, the low pressure of 20 MPa led to very small cells and a low cell density. The competition between the cell growth and cell nucleation played important role in the foam density and was directly related to the foaming temperature. Decreasing the infiltration temperature depressed the initial foaming temperature, and this resulted in significantly larger cells and a lower cell density. A short foaming time led to a skin–core structure; this indicated that a decrease in the cell size was found from skin to core, but the skin–core structure gradually disappeared with increasing foaming time. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Determination of modified polyamide 6's foaming windows by bubble growth simulations based on rheological measurements

Reactive extrusion was used to modify virgin polyamides 6 (v-PA6) and to prepare chain extended PA6 (CE-PA6) and long-chain branched PA6 (LCB-PA6) for the melt foaming process. This was done using a twin-screw extruder and the following modifiers: a chain extender ADR-4368 and a branching agent maleic anhydride grafted polypropylene. A reaction mechanism was proposed to explain the chain extension and long-chain branching reactions and was verified by the Fourier transform infrared spectroscopy data. The analysis of the gel permeation chromatography data showed that LCB-PA6 presented a strong increase in the molecular weight and in the dispersity index. Moreover, the rheological properties of the v-PA6 and modified PA6 resins were characterized by a dynamic shear test. The LCB-PA6 compared with CE-PA6 showed much higher shear viscosity and longer characteristic relaxation times, indicating the presence of an LCB structure. A uniaxial elongation test showed that the LCB-PA6 had the highest melt viscosity and melt strength as well as most obvious strain-hardening behavior. A high-pressure differential scanning calorimeter under compressed CO₂ was used to investigate the PA6's crystallization properties so as to analyze its minimum temperature of foaming windows. The melt foamability of the CE-PA6 and the LCB-PA6 was verified by batch melt foaming experiments with CO₂ as the blowing agent and maximum temperature of foaming windows was also quantitatively determined by numerical simulation of bubble growth based on the rheological measurements. The results showed that the LCB-PA6 foams had a smaller cell diameter, a larger cell density, a greater expansion ratio, and wider foaming temperature window than the CE-PA6. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48138.     

Effects of Process Variables on Microcellular Structure and Crystallization of Polypropylene Foams with Supercritical CO2 as the Foaming Agent—A Study of Microcellular Foaming of Polypropylene

The effects of process variables on the microcellular structure and crystallization of foamed polypropylene (PP) with supercritical CO₂ as the foaming agent were investigated in this article. The cell size increased and the cell density reduced with increased foaming temperature. Differently, both the cell diameter and cell density increased as saturation pressure increased. DSC curves showed that the melting peak was broadened when supercritical CO₂ foaming PP. Furthermore, the width at half-height of the melting peak increased, the melting peak moved to higher temperature, and the melting point and crystallinity enhanced as the foaming temperature lowered and the saturation pressure enhanced.     

Numerical simulation of bubble growth in viscoelastic fluid with diffusion of dissolved foaming agent

Viscoelastic simulations of bubble growth in polypropylene (PP) physical foaming were performed. A multimode Phan‐Thien Tanner (PTT) model was used to analyze the dynamic growth behavior of spherically symmetric bubbles with the diffusion of a foaming agent (CO₂). Changes in the dissolved foaming agent concentration in the polymer and in the strain of the polymer melt surrounding the bubbles were simulated with the Lagrangian FEM method. The simulation technique was validated by comparison with the bubble growth data, which were experimentally obtained from visual observations of the PP/CO₂ batch foaming system. The simulation results demonstrated that the strain‐hardening characteristic of polymer does not strongly affect the bubble growth rate. The linear viscoelastic characteristic is more influential, and the relaxation mode around 0.01 s is the most important factor in determining the bubble growth rate during the early stage of foaming. A multivariate analysis for the simulation results was also carried out. This clarified that bubble nucleus population density, surrounding pressure, initial dissolved foaming agent concentration, and diffusion coefficient are more important factors than the viscoelastic characteristics. POLYM. ENG. SCI., 45:1277–1287, 2005. © 2005 Society of Plastics Engineers     

Extrusion foaming behavior of a polypropylene/nanoclay microcellular foam

With maleic anhydride grafted polypropylene (PP‐g‐MAH) as a compatibilizer, composites of block‐copolymerized polypropylene (B‐PP)/nanoclay were prepared. The effects of the PP‐g‐MAH and nanoclay content on the crystallization and rheological properties of B‐PP were investigated. The microcellular foaming behavior of the B‐PP/nanoclay composite material was studied with a single‐screw extruder foaming system with supercritical (SC) carbon dioxide (CO₂) as the foaming agent. The experimental results show that the addition of nanoclay and PP‐g‐MAH decreased the melt strength and complex viscosity of B‐PP. When 3 wt % SC CO₂ was injected as the foaming agent for the extrusion foaming process, the introduction of nanoclay and PP‐g‐MAH significantly increased the expansion ratio of the obtained foamed samples as compared with that of the pure B‐PP matrix, lowered the die pressure, and increased the cell population density of the foamed samples to some extent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44094.     

Polydimethylsiloxane assisted supercritical CO<Subscript>2</Subscript> foaming behavior of high melt strength polypropylene grafted with styrene

Foamable high melt strength polypropylene (HMSPP) was prepared by grafting styrene (St) onto polypropylene (PP) and simultaneously introducing polydimethylsiloxane (PDMS) through a one-step melt extrusion process. The effect of PDMS viscosity on the foaming behavior of HMSPP was systematically investigated using supercritical CO₂ as the foaming agent. The results show that the addition of PDMS has little effect on the grafting reaction of St and HMSPP exhibits enhanced elastic response and obvious strain hardening effect. Though the CO₂ solubility of HMSPP with PDMS (PDMS-HMSPP) is lower than that of HMSPP without PDMS, especially for PDMS with low viscosity, the PDMS-HMSPP foams exhibit narrow cell size distribution and high cell density. The fracture morphology of PDMS-HMSPP shows that PDMS with low viscosity disperses more easily and uniformly in HMSPP matrix, leading to form small domains during the extrusion process. These small domains act as bubble nucleation sites and thus may be responsible for the improved foaming performance of HMSPP.

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The effect of dispersed elastomer particle size on heterogeneous nucleation of TPO with N2 foaming

Blending polypropylene (PP) with elastomeric modifiers provides a simple method of improving polymer's impact strength. Such PP/elastomer blends are commonly called thermoplastic polyolefin (TPO) blends. Developing TPO materials suitable for foaming is of great interest because they can be applied in high-volume markets such as the automotive industry. For immiscible polymer blends such as TPO, it has been often noted that the dispersed particles can act as cell nucleating agents, thereby enhancing heterogeneous nucleation. However, little work has been done to assess the effects of blend morphology on the nucleation behavior. Furthermore, the effects of elastomer dispersion on TPO foamability are still unknown. In this work, TPO blends with different blend morphologies were prepared by controlling the viscosity ratio between the blending components. Experimental results from both batch foaming and extrusion foaming processes with nitrogen (N₂) indicate that the foam structure is influenced by the size and the number density of the dispersed particles.     

Batch foaming of chain extended PLA with supercritical CO2: Influence of the rheological properties and the process parameters on the cellular structure

This study has been dedicated to the foaming of modified poly (lactic acid) with supercritical CO₂. The first part of this work consisted in a rheological modification of neat PLA through chain extension. Improvement of the melt viscosity and elasticity has been achieved by the use of an epoxy additive during a reactive extrusion process. Rheological characterizations confirmed an increase of the melt strength due to this chain extension process. Foaming was then performed on the neat and modified PLAs using a batch process with supercritical CO₂ as blowing agent. The investigation of the foaming temperature revealed an enlarged processing window for modified PLAs compared to neat PLA. Depending on the foaming parameters, foams with a cellular structure ranging from macro scale to micro scale have been obtained. A concomitant effect of the CO₂-plasticization and the crystallisation on the melt rheology could explain this wide range of cellular morphologies.