Effect of the introduction of polydimethylsiloxane on the foaming behavior of block‐copolymerized polypropylene

We investigated the effect of polydimethylsiloxane (PDMS) on the foaming properties of block‐copolymerized polypropylene (B‐PP) by blending different contents of PDMS with B‐PP in the extrusion process using supercritical CO₂ as the blowing agent. The experimental results indicate that the addition of PDMS greatly increased the expansion ratio of the foamed samples. At the same time, the cell population density of foams obtained from the blends also increased to a certain degree and provided a new perspective on improving B‐PP's foaming performance. The addition of PDMS also decreased the die pressure because of the reduced viscosity of the B‐PP/PDMS blends compared with that of the B‐PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polypropylene‐dispersed domain as potential nucleating agent in PS and PMMA solid‐state foaming

The potential of using dispersive domains in a polymer blend as a bubble nucleating agent was investigated by exploiting its high dispersibility in a matrix polymer in the molten state and its immiscibility in the solid state. In this experiments, polypropylene (PP) was used as the nucleating agent in polystyrene (PS) and poly(methyl methacrylate) (PMMA) foams at the weight fraction of 10, 20, and 30 wt %. PP creates highly dispersed domains in PS and PMMA matrices during the extrusion processing. The high diffusivity of the physical foaming agent, i.e., CO₂ in PP, and the high interfacial tension of PP with PS and PMMA could be beneficial for providing preferential bubble nucleation sites. The experimental results of the pressure quench solid‐state foaming of PS/PP and PMMA/PP blends verified that the dispersed PP could successfully increase the cell density over 10⁶ cells/cm³ for PS/PP and 10⁷ cells/cm³ for PMMA/PP blend and reduce the cell size to 24 μm for PS/PP and 9 μm for PMMA/PP blends foams. The higher interfacial tension between PP and the matrix polymer created a unique cell morphology where dispersed PP particles were trapped inside cells in the foam. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PP/PDMS共混物的连续挤出发泡成型

用二氧化碳作为发泡剂,利用串联发泡挤出系统研究了聚丙烯(PP)/聚二甲基硅氧烷(PDMS)混合物的膨胀比及泡孔密度,同时用马来酸酐接枝PP(PP-g-MAH)作为增容剂来提高PDMS与PP的相容性。结果表明,混合物的最大膨胀比可达25倍,而纯PP的最大膨胀比只有8倍。另外,与纯PP相比,混合物的泡孔密度显著提高(尤其是在低发泡剂浓度时)。     

A study of cell nucleation in the extrusion of polypropylene foams

An investigation has been performed of the cell nucleation and initial growth behaviors in the foam processing of polypropylene (PP) in both the linear and branched forms. These materials were foamed in extrusion with the two blowing agents, CO₂ and isopentane. The cell density generally increased with an increased content of the blowing agent, for both CO₂ and isopentane. The effect of processing pressure on the cell density was distinct when CO₂ was used, whereas no pressure effect was observed in the foam processing with isopentane. The cell morphologies for the two PPs were found to be significantly different. A slightly lower nuclei density was observed in the branched PP foams than in the linear PP foams. However, the phenomenon of cell coalescence was observed much less in the branched PP foams. Most cells in the branched PP foams were closed, whereas in the linear PP foams they were connected to each other. The experimental results indicated that the branched structure played an important role in determining the cell morphologies through its effects on the melt strength and/or melt elasticity.     

Cell coalescence suppressed by crosslinking structure in polypropylene microcellular foaming

A series of crosslinked polypropylene samples with increased melt strengths were prepared via a copolymerization reaction, followed by melt processing. These crosslinked PP samples (PP‐Cs) were foamed by a temperature rising process using supercritical CO₂ as the physical blowing agent. The introduction of crosslinking structure resulted in PP‐Cs foams with well‐defined closed cell structure, decreased cell size, and increased cell density in comparison with a linear PP, which were attributed to the suppressed cell coalescence due to the significant increase in melt strength of PP‐Cs. Further increasing the crosslinking degree tended to enhance the suppression effect on the cell coalescence, and hence increase the cell density of PP foams under the same foaming conditions, especially at the longer foaming times. The well‐defined closed cell structure was observed at the foaming temperature of 170–250°C and saturation pressure of 12–20 MPa. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Improving polypropylene microcellular foaming through blending and the addition of nano‐calcium carbonate

This article reports an attempt to improve polypropylene (PP) microcellular foaming through the blending of PP with high‐density polyethylene (HDPE) as a minor component and the incorporation of nano‐calcium carbonate (nano‐CaCO₃) into PP and its blends with HDPE. Three HDPEs were selected to form three blends with a viscosity ratio less than, close to, or greater than unity. Two concentrations of nano‐CaCO₃, 5 and 20 wt %, were used. The blends and nanocomposites were prepared with a twin‐screw extruder. The foaming was carried out by a batch process with supercritical carbon dioxide as a blowing agent. The online shear viscosity during compounding and the dynamic rheological properties of some samples used for foaming were measured. The cell structure of the foams was examined with scanning electron microscopy (SEM), and the morphological parameters of some foams were calculated from SEM micrographs. The rheological properties of samples were used to explain the resulting cell structure. The results showed that the blend with a viscosity ratio close to unity produced a microcellular foam with the minimum mean cell diameter (0.7 μm) and maximum cell density (1.17 × 10¹¹ cells/cm³) among the three blends. A foamed PP/nano‐CaCO₃ composite with 5 wt % nano‐CaCO₃ exhibited the largest cell density (8.4 × 10¹¹ cells/cm³). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Open‐cell foams of polyethylene terephthalate/bisphenol a polycarbonate blend

Open microcellular foams of polyethylene terephthalate (PET)/polycarbonate (PC) blends were prepared by controlling their foaming behavior at the interface between these two polymers. Interface modification was a crucial factor in governing the foaming behavior and cell morphology of the blend foams: annealing at 280°C, i.e., conducting the transesterification reaction, generates a PET‐b‐PC copolymer, which lowers the interfacial tension, increases the affinity between PET and PC, and decreases the crystallinity of the PET domains. When CO₂ foaming was performed at the interface modified with the copolymer, an interesting fibril‐like structure was formed. The cell density of the PET/PC blend then increased, and its cell size reduced to the microscale while maintaining a high open‐cell ratio. The effect of heat annealing (transesterification reaction) on CO₂‐foaming was studied to reveal the relationship among the interface affinity, crystallinity, and degree of fibrillation. The optimal heat‐annealing procedure generated a fibril‐like structure in the PET/PC blend foams with a high cell density (7 × 10¹¹ cm^?3), small cell size (less than 2 μm), and 100% open‐cell ratio. POLYM. ENG. SCI., 55:375–385, 2015. © 2014 Society of Plastics Engineers     

Temperature influence and CO2 transport in foaming processes of poly(methyl methacrylate)–block copolymer nanocellular and microcellular foams

Fabricated by high-pressure or supercritical CO₂ gas dissolution foaming process, nanocellular and microcellular polymer foams based on poly(methyl methacrylate) (PMMA homopolymer) present a controlled nucleation mechanism by the addition of a methylmethacrylate–butylacrylate–methylmethacrylate block copolymer (MAM), leading to defined nanocellular morphologies templated by the nanostructuration of PMMA/MAM precursor blends. Influence of the CO₂ saturation temperature on the foaming mechanism and on the foam structure has been studied in 90/10 PMMA/MAM blends and also in the neat (amorphous) PMMA or (nanostructured) MAM polymers, in order to understand the role of the MAM nanostructuration in the cell growth and coalescence phenomena. CO₂ uptake and desorption measurements on series of block copolymer/homopolymer blend samples show a competitive behavior of the soft, rubbery, and CO₂-philic block of PBA (poly(butyl acrylate)) domains: fast desorption kinetics but higher initial saturation. This competition nevertheless is strongly influenced by the type of dispersion of PBA (e.g. micellar or lamellar) and a very consequent influence on foaming.CO₂ sorption and desorption were characterized in order to provide a better understanding of the role of the block copolymer on the foaming stages. Poly(butyl acrylate) blocks are shown to have a faster CO₂ diffusion rate than poly(methyl methacrylate) but are more CO₂-philic. Thus gas saturation and cell nucleation (heterogeneous) are more affected by the PBA block while cell coalescence is more affected by the PMMA phases (in the copolymer blocks + in the matrix).     

A simple method for preparation of polymer microcellular foams by in situ generation of supercritical carbon dioxide from dry ice

In this work, poly(methyl methacrylate) (PMMA) and PMMA/nanoclay nanocomposite microcellular foams were successfully prepared using a simple method based on in situ generation of supercritical carbon dioxide (CO₂) from dry ice. The method was compared with conventional methods exempted from high pressure pump and a separate CO₂ tank. Effect of various processing conditions such as saturation temperature and pressure and clay concentration on cellular morphology and hardness of the prepared microcellular foams was examined. State of the clay dispersion in the prepared PMMA/clay nanocomposites was characterized using X-ray diffraction and transmission electron microscopy techniques. Field emission scanning electron microscopy was used to study cellular morphology of the prepared foams. It was observed that elevation of saturation temperature from 85 to 105 °C at constant saturation pressure increased cell density and decreased average cell size of the prepared PMMA foams. Furthermore, an increase in saturation pressure from 120 to 180 bar resulted in a reduction in average cell diameter and an increase in cell density of the prepared PMMA foams. On the basis of the gathered results, optimum conditions for preparation of PMMA microcellular foams were determined and applied for preparation of PMMA/nanoclay microcellular foams. It was shown that incorporation of clay into the polymer matrix resulted in a finer and more uniform cellular morphology in the final microcellular foams. It was also observed that incorporation of nanoclay into the prepared foams, up to 3 wt%, led to a moderate increase in the foam hardness.     

Linear viscoelastic behavior of compatibilized PMMA/PP blends

In this work, the morphology and linear viscoelastic behavior of PMMA/PP blends to which a graft copolymer PP‐g‐PMMA has been added was studied. The copolymer concentration varied from 1 to 10 wt % relative to the dispersed phase concentration. The rheological data were used to infer the interfacial tension between the blended components. It was observed that PP‐g‐PMMA was effective as a compatibilizer for PMMA/PP blends. For PP‐g‐PMMA concentration added below the critical concentration of interface saturation, two rheological behaviors were observed depending on the blend concentration: for 70/30 blend, the storage modulus, at low frequencies, increased as compared to the one of the unmodified blend; for 90/10 blend, it decreased. For 90/10 blend, the relaxation spectrum presented an interfacial relaxation time related to the presence of the compatibilizer (τ_β). For PP‐g‐PMMA concentrations added above the critical concentration of interface saturation, the storage modulus of all blends increased as compared with the one of the unmodified blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Nanoscale Cellular Foams from a Poly(propylene)‐Rubber Blend

Plastic foams with nano/micro‐scale cellular structures were prepared from poly(propylene)/thermoplastic polystyrene elastomer (PP/TPS) systems, specifically the copolymer blends PP/hydrogenated polystyrene‐block‐polybutadiene‐block‐polystyrene rubber and PP/hydrogenated polystyrene‐block‐polyisoprene‐block‐polystyrene. These PP/TPS systems have the unique characteristic that the elastomer domain can be highly dispersed and oriented in the machine direction by changing the draw‐down ratio in the extrusion process. A temperature‐quench batch physical foaming method was used to foam these two systems with CO₂. The cell size and location were highly controlled in the dispersed elastomer domains by exploiting the differences in CO₂ solubility, diffusivity, and viscoelasticity between the elastomer domains and the PP matrix. The average cell diameter of the PP/TPS blend foams was controlled to be 200–400 nm on the finest level by manipulating the PP/rubber ratio, the draw‐down ratio of extrusion and the foaming temperature. Furthermore, the cellular structure could be highly oriented in one direction by using the highly‐oriented elastomer domains in the polymer blend morphology as a template for foaming.

     

加工参数及配方对PP/SBS共混物泡孔形态的影响

以CO2为发泡剂,利用SEM、DSC等测试方法研究了聚丙烯/苯乙烯-丁二烯-苯乙烯共聚物(PP/SBS)共混物的发泡行为。结果表明:在PP基体中引入SBS能显著改善发泡样品的泡孔形态;引入聚二甲基硅氧烷(PDMS)后,共混物的泡孔尺寸降低,泡孔密度进一步增大;在高压力降速率下,共混物的泡孔形态进一步改善;当发泡温度降到105℃时,由于CO2的增塑作用,PP/SBS/PDMS共混物仍能充分发泡,而且泡孔结构更好,其泡孔密度3.4×109个/cm3,平均泡孔直径6μm左右。     

Supercritical CO2-assisted extrusion foaming: A suitable process to produce very lightweight acrylic polymer micro foams

A strategy of CO₂-assisted extrusion foaming of PMMA-based materials was established to minimize both foam density and porosities dimension. First a highly CO₂-philic block copolymer (MAM: PMMA-PBA-PMMA) was added in PMMA in order to improve CO₂ saturation before foaming. Then the extruding conditions were optimized to maximize CO₂ uptake and prevent coalescence. The extruding temperature reduction led to an increase of pressure in the barrel, favorable to cell size reduction. With the combination of material formulation and extruding strategy, very lightweight homogeneous foams with small porosities have been produced. Lightest PMMA micro foams (ρ = 0.06 g cm⁻³) are demonstrated with 7 wt% CO₂ at 130°C and lightest blend micro foams (ρ = 0.04 g cm⁻³) are obtained at lower temperature (110°C, 7.7 wt% CO₂). If MAM allows a reduction of T^foaming, it also allows a much better cell homogeneity, an increase in cell density (e.g., from 3.6 10⁷ cells cm⁻³ to 2 to 6 10⁸ cells cm⁻³) and an overall decrease in cell size (from 100 to 40 μm). These acrylic foams produced through scCO₂-assisted extrusion has a much lower density than those ever produced in batch (ρ ≥ 0.2 g cm⁻³).     

Open‐cell polypropylene/polyolefin elastomer blend foams fabricated for reusable oil‐sorption materials

The fabrication of high‐performance oil sorbents is of great significance for oil spill cleanup. The main objective of this study was to prepare open‐cell polypropylene/polyolefin elastomer (PP/POE) blend foams for fabrication of reusable sorbents for oil sorption. Open‐cell PP/POE blend foams were prepared via continuous‐extrusion foaming using supercritical carbon dioxide as the blowing agent. The interconnected open‐cell structure was characterized by scanning electron microscopy. The hydrophobicity and lipophilicity of PP/POE open‐cell foams were revealed by tests of contact‐angle measurement, water and cyclohexane sorption on the foam surface, CCl₄ and cyclohexane sorption in water, and oil/water separation. Further, the sorption tests indicated that PP/POE blend foams showed larger oil‐uptake capacities than pure PP foams. In addition, cyclic compression tests showed that PP/POE open‐cell foams had excellent ductility and significantly improved recoverability compared to pure PP foams. In cyclic sorption–desorption tests, the sorption kinetics was studied in terms of capacity and saturation time, showing that PP/POE foams kept larger sorption capacities for 10 cycles, with larger sorption rates and good reusability. Based on the high open‐cell content, the good hydrophobic and oleophilic properties, the high oil‐sorption capacity, the improved recoverability, the large sorption rate, and the good reusability in cyclic oil‐sorption performance, the PP/POE open‐cell foams have shown promise as potential oil sorbents in applications for oil spill cleanup. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43812.     

High-energy mechanical alloying of thermoplastic polymers in carbon dioxide

High-energy ball milling was performed on low density polyethylene (LDPE) and isotactic polypropylene (iPP) as well as on 20/80 binary mixture of both polymers. Mechanical alloying was carried out at high pressure with carbon dioxide for a short period. The presence of CO₂ avoids oxidative mechano-chemical degradation of polymers and enhances the effectiveness of the milling. The effects of the mechano-chemical treatment on the molecular and physical properties of both single polymers and blends of intrinsically incompatible polymers were explored by FTIR spectroscopy, thermal analysis, intrinsic viscosity determination and solvent fractionation. Structural changes on PP and PP/LDPE blend were observed and have a strong dependence on the milling time. Mechanical tests confirm an overall improvement in blend properties by mechanical alloying. Experimental evidences are presented to suggest that CO₂ high-energy ball milling causes a self-compatibilization of the blend LDPE-iPP by breaking iPP polymer chains and allowing them to recombine with the neighboring LDPE chains.     

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     

Microcellular foam of polymer blends of HDPE/PP and their composites with wood fiber

In this study, the effects of batch processing conditions (foaming time and temperature) and blend composition as well as the effect of incorporating wood fiber into the blends on the crystallinity, sorption behavior of CO₂, void fraction, and cellular morphology of microcellular foamed high‐density polyethylene (HDPE)/polypropylene (PP) blends and their composites with wood fiber were studied. Blending decreased the crystallinity of HDPE and PP and facilitated microcellular foam production in blend materials. The void fraction was strongly dependent on the processing conditions and on blend composition. Foamed samples with a high void fraction were not always microcellular. The addition of wood fiber inhibited microcellular foaming. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2842–2850, 2003     

Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process

Use of supercritical carbon dioxide (scCO₂) as a blowing agent to generate microcellular polymer foams (MPFs) has recently received considerable attention due to environmental concerns associated with conventional organic blowing agents. While such foams derived from amorphous thermoplastics have been previously realized, semicrystalline MPFs have not yet been produced in a continuous scCO₂ process. This work describes the foaming of highly crystalline poly(vinylidene fluoride) (PVDF) and its blends with amorphous polymers during extrusion. Foams composed of neat PVDF and immiscible blends of PVDF with polystyrene exhibit poor cell characteristics, whereas miscible blends of PVDF with poly(methyl methacrylate) (PMMA) yield foams possessing vastly improved morphologies. The results reported herein illustrate the effects of blend composition and scCO₂ solubility on PVDF/PMMA melt viscosity, which decreases markedly with increasing PMMA content and scCO₂ concentration. Morphological characterization of microcellular PVDF/PMMA foams reveals that the cell density increases as the PMMA fraction is increased and the foaming temperature is decreased. This study confirms that novel MPFs derived continuously from semicrystalline polymers in the presence of scCO₂ can be achieved through judicious polymer blending.     

Physicomechanical,friction, and abrasion properties of EVA/PU blend foams foamed by supercritical nitrogen

Elastomer foams based on EVA, PU, and EVA/PU blends formulated for shoe‐sole applications were prepared by a supercritical N₂ batch foaming process and characterized for physicomechanical, friction and abrasion properties. The blending of EVA with PU was aimed for improving the friction and wear characteristics of the EVA based foams. All of the foams prepared showed spherical cells with closed‐cell morphology and the cell sizes varied with varying the EVA/PU blend ratio and CaCO₃ content of the foams. The properties such as hardness and resilience, friction coefficients and abrasion resistance improved for the EVA/PU blend foams compared to the EVA foam, but their compression set, tensile strength, and tear strength were inferior to the EVA foam. The incorporation of CaCO₃ filler increased density, hardness, tensile strength, and tear strength of the EVA/PU blend foams but decreased resilience, compression set, friction coefficients, and abrasion resistance. The improvement in friction coefficients and wear resistance obtained in the EVA/PU blend foams was significant for shoe‐sole applications. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers