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 long chain branches on the crystallization and foaming behaviors of polypropylene-g-poly(ethylene-co-1-butene) graft copolymers with well-defined molecular structures

A series of polypropylene-g-poly(ethylene-co-1-butene) graft copolymers (PP-g-EBR) with well-defined long chain branched (LCB) molecular structures, basing on the same PP–BT precursor (PP–BT2), were used to study effects of EBR LCBs on the crystallization and foaming behaviors of PP-g-EBRs. The kinetics results of isothermal and nonisothermal crystallization verify the opposite effects of LCB structure on the crystallization process of PP backbones in PP-g-EBRs: on one hand, the indolent LCB structure can perform the function of heterogeneous nucleation to facilitate the crystallization; on the other hand, the mobility and reptation ability of PP backbones are restrained by the LCB structure, which hinders the crystallization process. Additionally, the fluctuation-assisted nucleation mechanism caused by microphase separation between the EBR rich phase and the PP rich phase may account, to some extent, for the heterogeneous nucleation effect. The PP–BT2 and PP-g-EBRs were foamed by a batch method under the same conditions, using supercritical CO₂ as blowing agent. The resulting PP-g-EBR foams exhibited closed cell structure and increased cell density compared to the PP–BT2 foam, attributing to the enhanced melt strength. The cell density of PP-g-EBR foam increased first and decreased then with the LCB level increasing. The influence of LCB level on cell size was somewhat complex. Increasing LCB level, which promoted melt strength and strain hardening behavior of PP-g-EBRs, decreased the cell size and narrowed the cell size distribution. However, large cells were observed in PP-g-EBR foams with relatively high LCB level, which could be ascribed to the larger growing space introduced by the higher content of amorphous EBR LCBs. Moreover, the melting behaviors of PP–BT2 and PP-g-EBRs before and after foaming treatment were compared.     

Rheology and extrusion foaming of chain‐branched poly(lactic acid)

In this study, the effect of macromolecular chain‐branching on poly(lactic acid) (PLA) rheology, crystallization, and extrusion foaming was investigated. Two PLA grades, an amorphous and a semi‐crystalline one, were branched using a multifunctional styrene‐acrylic‐epoxy copolymer. The branching of PLA and its foaming were achieved in one‐step extrusion process. Carbon dioxide (CO₂), in concentration up to 9%, was used as expansion agent to obtain foams from the two PLA branched using chain‐extender contents up to 2%. The foams were investigated with respect to their shear and elongational behavior, crystallinity, morphology, and density. The addition of the chain‐extender led to an increase in complex viscosity, elasticity, elongational viscosity, and in the manifestation of the strain‐hardening phenomena. Low‐density foams were obtained at 5–9% CO₂ for semi‐crystalline PLA and only at 9% CO₂ in the case of the amorphous PLA. Differences in foaming behavior were attributed to crystallites formation during the foaming process. The rheological and structural changes associated with PLA chain‐extension lowered the achieved crystallinity but slightly improved the foamability at low CO₂ content. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Influence of extrusion temperature on molecular architecture and crystallization behavior of peroxide‐induced slightly crosslinked poly(L‐lactide) by reactive extrusion

The influence of temperature during reactive extrusion of poly(L ‐lactide) (PLLA) on the molecular architecture and crystallization behavior was investigated for OO‐(t‐butyl) O‐(2‐ethylhexyl) peroxycarbonate‐modified polymer. The long chain–branched PLLA (LCB‐PLLA) content and its structure in the resulting slightly crosslinked PLLA (χ‐PLLA) containing linear and LCB‐PLLA were characterized by both analyses, size exclusion chromatography equipped with multiangle laser light scattering and rheological measurements. A reduction of LCB‐PLLA content in χ‐PLLA and an increase of number of branches in LCB‐PLLA were found with increasing the extrusion temperature. An increase of extrusion temperature induces different process in the polymer: decrease of the lifetime of peroxide, increase of the radical concentration due to rapid peroxide decomposition rate, and increase of the chain diffusion to the amorphous phase. Among these indices, the lifetime of peroxide is a good index for crosslinking behavior of PLLA during extrusion. As for the isothermal crystallization behavior from the melt, the Avrami crystallization rate constant of χ‐PLLA increases as an increase of LCB‐PLLA content in χ‐PLLA. This implies that LCB‐PLLA acts as a nucleating agent for PLLA. Furthermore, regime analysis and the free energy of nucleus of χ‐PLLA were investigated using Hoffman–Lauritzen theory. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Recycling of poly(ethylene terephthalate) into closed‐cell foams

The increase of the elongational viscosity of recycled poly(ethylene terephthalate) (PET) is investigated with the aim of producing closed‐cell foams by means of a cost‐effective reactive extrusion technique. A recycled PET grade containing controlled contamination levels of polyvinyl chloride (PVC) and poylethylene (PE) is selected, and compared with virgin bottle‐grade PET as a reference. Reactive processing with a tetrafunctional epoxy additive induces randomly branched molecules with a lower degree of branching in recycled PET than in virgin PET, as shown by a molecular structure analysis. The corresponding increase in elongational viscosity is related to foaming experiments performed using supercritical CO₂ in a pressurized vessel. Observations of foam microstructures reveal that modified virgin PET forms closed‐cell structures under a large variety of foaming conditions, as opposed to unmodified virgin and recycled PET, which collapse as a result of insufficient elongational resistance. Closed‐cell foams are also obtained using modified recycled PET, providing that the temperature at which the pressure is released is lowered to 260°. Recycling of PET into closed‐cell foams is thus achieved, although the processing window is slightly reduced compared to virgin PET.     

Melt foamability of reactive extrusion‐modified poly(ethylene terephthalate) with pyromellitic dianhydride using supercritical carbon dioxide as blowing agent

By reactive extrusion with pyromellitic dianhydride (PMDA), foamable poly(ethylene terephthalate) (PET) was obtained, which achieved a maximum intrinsic viscosity of 1.36 dL/g with PMDA content 0.8 wt%. Dynamic shear rheological properties were measured to characterize the structure evolution of modified PET. And the Avrami analysis was extended for the non‐isothermal crystallization process of modified PET, which relates to cell stabilization in the melt foaming process. Based on the batch foaming process with supercritical carbon dioxide as blowing agent, broad foaming temperature windows were obtained for PETs modified with 0.8 and 0.5 wt% PMDA, in which PET foams with the expansion ratio between 10 and 50 times, the cell diameter between 15 and 37 μm, and the cell density between 6.2 × 10⁸ and 1.6 × 10⁹ cells/cm³ were controllably produced. POLYM. ENG. SCI., 55:1528–1535, 2015. © 2014 Society of Plastics Engineers     

Integrated process of supercritical CO2-assisted melt polycondensation modification and foaming of poly(ethylene terephthalate)

An integrated process of melt polycondensation modification and foaming of poly(ethylene terephthalate) (PET) was performed in a high pressure vessel assisted by supercritical carbon dioxide (scCO₂). ScCO₂ was firstly employed to sweep PET melt, i.e., high pressure CO₂ continuously flows through the vessel at a fixed flow rate to remove small molecules for higher molecular weight PET, then this modified PET melt was directly foamed through a rapid depressurization process using scCO₂ as blowing agent. In this integrated process, PET with high melt strength after polycondensation modification could be foamed directly in molten state. Therefore, re-molten process of solid modified PET pellets was canceled to avoid its degradation and CO₂ saturation time could be saved in foaming process, thus processing time could be shortened and energy efficiency could be improved. The influences of scCO₂ sweeping treatment time, pressure and flow rate on properties of the modified PETs and cell morphologies of the foamed PETs were investigated respectively. The results showed that CO₂ sweeping treatment could effectively enhance PET melt polycondensation modification process, which was superior to that of N₂ treatment. PET foams with average cell diameter of 32–62 μm and cell density of 1 × 10⁷ to 4 × 10⁷ cells/cm³ have been obtained in the integrated process. Compared with the process of only foaming modified PET by scCO₂ or performing scCO₂ assisted modified PET further melt polycondensation process and scCO₂ foaming process separately, this integrated process produced better cell morphology.     

Extruded polystyrene foams with bimodal cell morphology

Extrusion foaming using supercritical carbon dioxide (CO₂) as the blowing agent is an economically and environmentally benign process. However, it is difficult to control the foam morphology and maintain its high thermal insulation comparing to the conventional foams based on fluorocarbon blowing agents. In this study, we demonstrated that polystyrene (PS) foams with the bimodal cell morphology can be produced in the extrusion foaming process using CO₂ and water as co-blowing agents and two particulate additives as nucleation agents. One particulate is able to decrease the water foaming time so both CO₂ and water can induce foaming simultaneously, while the other increases the CO₂ nucleation rate with little effect on the CO₂ foaming time. Our experimental results showed that a dual particulate combination of nanoclay and activated carbon provided the best bimodal structure. The bimodal foams exhibited much better compressive properties and slightly better thermal insulation for PS foams.     

Controlling sandwich‐structure of PET microcellular foams using coupling of CO2 diffusion and induced crystallization

Controlling sandwich‐structure of poly(ethylene terephthalate) (PET) microcellular foams using coupling of CO₂ diffusion and CO₂‐induced crystallization is presented in this article. The intrinsic kinetics of CO₂‐induced crystallization of amorphous PET at 25°C and different CO₂ pressures were detected using in situ high‐pressure Fourier transform infrared spectroscopy and correlated by Avrami equation. Sorption of CO₂ in PET was measured using magnetic suspension balance and the diffusivity determined by Fick's second law. A model coupling CO₂ diffusion in and CO₂‐induced crystallization of PET was proposed to calculate the CO₂ concentration as well as crystallinity distributions in PET sheet at different saturation times. It was revealed that a sandwich crystallization structure could be built in PET sheet, based on which a solid‐state foaming process was used to manipulate the sandwich‐structure of PET microcellular foams with two microcellular or even ultra‐microcellular foamed crystalline layers outside and a microcellular foamed amorphous layer inside. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2512–2523, 2012     

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.     

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.     

High‐melt‐elasticity poly(ethylene terephthalate) produced by reactive extrusion with a multi‐functional epoxide for foaming

A multi‐functional epoxide oligomer, Joncryl ADR‐4368 (ADR), is used as a modifier to prepare foamable poly(ethylene terephthalate) (PET) by reactive extrusion and compared with common tetra‐functional modifier pyromellitic anhydride (PMDA) as a reference. Torque evolution reveals that ADR has a faster reaction with PET than PMDA. The reactions generate long‐chain branches and gel structures, which are confirmed by rheological methods. Shear rheological studies show that PET modified with both ADR and PMDA display higher complex viscosity and lower loss tangent than unmodified sample. In particular, at a given viscosity level, ADR leads to a lower loss tangent than PMDA. Moreover, compared to PMDA, the addition of ADR results in a higher die pressure during extrusion and a more pronounced strain hardening during uniaxial elongation. These results indicate that ADR‐modified PET is less viscous but more elastic than PMDA‐modified PET. Owing to the higher elastic properties, ADR‐modified PET presents better foaming performance in batch foaming process with CO₂ as a blowing agent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45805.     

Reactive modification of PBT with applications in low density extrusion foaming

By contrast to polyethylene terephthalate (PET), extrusion foaming of polybutylene terephthalate (PBT) to medium–low densities has been seldom reported in the literature. In this study, a commercial linear PBT resin was reactively modified in a batch mixer to a branched structure with a higher molecular weight (MW) and a broader molecular weight distribution (MWD) as evidenced by rheological analysis. Chain branching was also accomplished by single screw extrusion, where the competing degradation reaction needed to be taken into account. Optimization of the extrusion operational conditions, which also involved the use of suitable consititutive equations, led to the production of a branched resin with viscoelastic characteristics suitable for low density extrusion foaming by injection of physical blowing agents (PBA). The branched product made under the optimized conditions showed good foamability. The effect of pressure drop rate on cell nucleation rate and the effect of the crystallization rate on cell density and cell morphology are examined. POLYM. ENG. SCI., 47:244–253, 2007. © 2007 Society of Plastics Engineers.     

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     

Foaming of linear isotactic polypropylene based on its non-isothermal crystallization behaviors under compressed CO2

The non-isothermal crystallization behaviors of isotactic polypropylene (iPP) under ambient N₂ and compressed CO₂ (5–50 bar) at cooling rates of 0.2–5.0 °C/min were carefully studied using high-pressure differential scanning calorimeter. The presence of compressed CO₂ had strong plasticization effect on the iPP matrix and retarded the formation of critical size nuclei, which effectively postponed the crystallization peak to lower temperature region. On the basis of these findings, a new foaming strategy was utilized to fabricate iPP foams using the ordinary unmodified linear iPP with supercritical CO₂ as the foaming agent. The foaming temperature range of this strategy was determined to be as wide as 40 °C and the upper and lower temperature limits were 155 and 105 °C, which were determined by the melt strength and crystallization temperature of the iPP specimen under supercritical CO₂, respectively. Due to the acute depression of CO₂ solubility in the iPP matrix during the foaming process, the iPP foams with the bi-modal cell structure were fabricated.     

Influence of crystallization on microcellular foaming behavior of polyamide 6 in a supercritical CO2-assisted route

Supercritical CO₂ as a blowing agent has attracted increasing interest in the preparation of microcellular polyamide 6 (PA6) foams. In this work, we developed the supercritical CO₂-assisted method to prepare a series of different microcellular PA6 foams by controlling its crystallization properties in two steps and carefully investigated the corresponding crystallization properties of modified PA6 and foams using various techniques. Initially, a multifunctional epoxy-based chain extender (CE) was used to produce high-melt strength-modified PA6 with improved foaming ability; then, the resulting PA6 was foamed to prepare the microcellular foams of PA6 using supercritical CO₂ as a blowing agent in a batch foaming route. The CE effectively enhanced the melt strength of PA6, and CE usage was optimized to obtain a threshold of high branching without crosslinking. The number of crystals was also adjusted by the saturation temperature. Furthermore, these crystals that formed during the saturation process served as high-efficiency bubble nucleating agents and then limited the growth of bubbles at the same time. The microcellular foams of PA6 were successfully obtained with a cell size of 10.0 μm, and cell density of 2.0 × 10⁹ cells/cm³ at the saturation temperature of 225°C.     

Rheological control in foaming polymeric materials: II. Semi-crystalline polymers

The influence of rheological properties and crystallization on foam structures, such as cell diameter, cell density and cell size distribution, of semi-crystalline polymer was investigated. The rheological properties of polypropylene (PP) were controlled by long chain branching (LCB) modification with free radical reaction and its crystallinity. The foaming behavior could be well correlated with the crystal structure and the rheological properties of polymers. The results showed that the long chain branching modification changed the crystallization speed, the diameter and the number of crystal and the rheological behavior as well. The interplay between the crystallization and the rheology of polymers with different chain structures can cause different nucleation mechanism in foaming. Both the cell size of linear PP and LCB PP decrease with crystallization time, and the cell density increases with crystallization time. The crystals in PPs acted as heterogeneous nucleation cites for bubbles, but the cell density of LCB PP is much higher than that of linear PP because of it higher spherulites density. The higher viscosity of branched PP further made its cell diameter smaller than that of linear one. Therefore, the foam structure can be well controlled by tuning the chain structure and crystal structures.     

Rheological,crystallization and foaming behaviors of high melt strength polypropylene in the presence of polyvinyl acetate

Polyvinyl acetate (PVAc) is a kind of CO₂-philic materials with high solubility of CO₂. For improving the supercritical carbon dioxide (Sc-CO₂) foaming behavior of isotactic polypropylene (iPP), a high melt strength polypropylene (HMSPP) was prepared using styrene (St) as grafting monomer. The effect of PVAc on the preparation, rheological, crystallization and foaming behaviors of HMSPP was investigated. The high temperature gel permeation chromatography (HT-GPC) results showed that the PVAc had a promotive effect on melt grafting reaction. With the addition of PVAc, the weight-average molecular weight (M_w) of HMSPP increased from 217,158 to 240,733 g/mol. Thus, the HMSPP presented higher complex viscosity and storage modular, and lower loss angle, which indicated that the melt viscosity and melt strength of HMSPP was increased by adding PVAc. The crystallization behavior of HMSPP was investigated using differential scanning calorimetry (DSC). Double crystallization peaks were observed on the DSC cooling curves of HMSPP in the presence of PVAc, which was ascribed to incomplete molten of iPP with long chain branching (LCB) structure at low end melting temperature. Moreover, the prepared HMSPP exhibited better foaming behavior in the presence of PVAc. With the addition of PVAc, the average cell diameter of HMSPP decreased from 93 to 59 μm, and the cell density increased from 2.83?×?10⁷ to 9.79?×?10⁷ cell/cm³.     

Rheological control in foaming polymeric materials: I. Amorphous polymers

The influence of rheological properties, especially melt strength, on foam structures, such as cell size, cell density and cell size distribution, of amorphous polymer was investigated. The rheology of polystyrene (PS) was controlled by molecular modification with free radical reaction, and PS with long chain branching (LCB) level ranging from 0.15 to 1.6 branching point per 10⁴ carbon atom was gotten. The shear and elongational rheology were found to be dependent on the LCB structure, and the strain hardening behavior of modified samples in transient elongational viscosity confirmed the existence of long branched chain. The effects of chain structure and foaming conditions such as temperature and pressure were studied by the analysis on the foam structures obtained by supercritical CO₂. The experimental results revealed that increasing LCB level would decrease cell size, make cell size distribution narrower and slightly increase cell density. The effects of chain topology on the foam structures were also investigated by numerical simulation, where Pom-Pom model was used to describe the effect of backbone length and arm length. The dependence of cell size on the arm length was consistently observed in experiments and simulation. It suggested that the arm length had greater influence on the cell radius than the backbone length. Therefore, the relationship among foam structures, rheological properties and molecular structures can be established from both experiments and simulation, which can be used as a guidance to control the foam structure by designing and controlling the molecular structures and the corresponding rheological properties.     

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.