CO2‐induced crystal engineering of polylactide and the development of a polymeric nacreous microstructure

Nacre's biomineralization process and its self‐organizing brick‐and‐mortar crystalline microstructure have inspired many researchers to develop new materials derived from the natural world. In our study, we took a novel approach to two‐dimensional (2‐D) crystallization. That is, we applied the biomineralization self‐organizational principle that exists in natural materials to a biopolymer (polylactide). The CO₂‐induced crystallization of poly(d ‐lactide), with its unique diffusion‐controlled crystallization mechanism, tends to produce distinct 2‐D spherulitic structures. We found that these 2‐D spherulites were self‐organizing in nature, and that they created a stack of 2‐D spherulitic structures. These crystalline microstructures, with their intervening amorphous phase, were foamed in situ due to the CO₂‐induced crystallization self‐exclusion phenomenon. We compared the resultant crystalline structure with nacre's brick‐and‐mortar crystalline microstructure to confirm the biomimetic principle of self‐organization. To the best of our knowledge, this is the first time that a biopolymer has been crystallized in a 2‐D manner in a way that resembles nature's biomineralization process. The hierarchical crystalline microstructure is morphologically similar to that of nacre biomaterials. This novel crystallization technique is simple, absolutely non‐toxic and works swiftly to produce a brick‐and‐mortar crystalline microstructure with a high degree of order. © 2017 Society of Chemical Industry     

Effect of crystallinity on unimodal and bimodal cell structures,in a continuous production of HDPE microcellular foamed sheets using supercritical CO2 (ScCO2)

Crystallinity is a controlling parameter in the development of microcellular foam final structure. In this research, using a well-controlled continuous microcellular foamed sheet production system, the effect of crystallinity on the final structure of the microcellular foam is studied. To produce microcellular foamed sheets, different levels of the supercritical carbon dioxide (ScCO₂) is dissolved in the polymer at high pressure and the foamed material is stabilized using a four roll apparatus at different roll temperatures. Crystallization occur by delay, however this lag time can be controlled by controlling temperature gradient. The higher decrease in the roll temperature results in higher temperature gradient which increases the crystallization rate during the cell growth, causing bimodal cell structures which indicates secondary nucleation. Moreover, as the amount of gas increases, the cell formation time increases, hence, at even higher temperatures we observed the effect of secondary nucleation, resulting in the occurrence of bimodal cell structures.     

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.     

Effects of processing parameters and thermal history on microcellular foaming behaviors of PEEK using supercritical CO2

In this study, we mainly investigate the solid‐state foaming of polyether ether ketone (PEEK) with different crystallinities using supercritical CO₂ as a physical blowing agent. The gaseous mass‐transfer and thermophysical behaviors were studied. By altering the parameters of the foaming process, microcellular foams with different cell morphologies were prepared. The effect of crystallization on the cell morphology was also investigated in detail. The results indicate that the crystallization restricts gas diffusion in the material, and the thermophysical behaviors of the saturated PEEK sample with low crystallinity presents two cold crystallization peaks. The cell density decreases and the cell size increases as the saturation pressure increases. The cell density of the microcellular foams prepared under 20 MPa is 1.23 × 10¹⁰ cells/cm³, which is almost 10 times compares to that under 8 MPa. The cell size increases as the foaming time extends or the foaming temperature increases. It is interesting that the cell morphology with a bimodal cell‐size distribution is generated when the samples are foamed at temperatures higher than 320°C for a sufficient time. Additionally, nanocellular foams can be obtained from a highly crystallized PEEK after the decrystallization process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42576.     

Effect of the molecular weight between crosslinks of thermally cured epoxy resins on the CO2‐bubble nucleation in a batch physical foaming process

Epoxy resins (bisphenol A type epoxy resins/2‐ethyl‐4‐methylimidazole) consisting of oligomers with different molecular weights were foamed using a temperature‐quench physical foaming method with CO₂. The resulting cell morphologies could be classified into four types: non‐foamed structure, cracked structure, star‐shaped structure, and sphere‐shaped structure. The effects of the gel fraction and molecular weight between crosslinks (M_C) on the cell morphology were investigated for the preparation of microcellular epoxy foams. M_C was calculated by measuring the plateau rubber modulus of the rheological properties and the weight uptake of acetone. By varying the molecular weight of the epoxy oligomers and the cure time, the M_C of the epoxy was controlled to modulate the cell morphology. The experiments elucidated the threshold M_C value that permits CO₂‐bubble nucleation: CO₂‐bubble nucleation in the epoxy resin could be induced when the distance between the crosslinking points exceeded the critical size of bubble nucleus. Based on this information, the microcellular epoxy foam was prepared by maintaining M_C above 10⁴g mol⁻¹ and the complex modulus above 6 × 10⁸ Pa. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40407.     

Microcellular foams of glass–fiber reinforced poly(phenylene sulfide) composites generated using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide) (PPS) and its glass–fiber (GF) reinforced composites using supercritical CO₂ as a blowing agent presents a promising approach to produce novel cellular materials with tailored microstructures. This study investigated the effects of the material composition and process conditions on the foaming behaviors and final morphologies of the microcellular foamed PPS and PPS/GF composites. The rheological and thermal properties as well as the saturation and desorption behaviors of CO₂ in the pure PPS and PPS/GF composites were also detailedly discussed. The results show that microcellular foams with various relative densities, cell sizes, cell‐size distributions, and cell densities can be attained by tailoring the fiber content and key process parameters. At low foaming temperatures below the cold crystallization temperature, the microcellular foamed PPS and PPS/GF composites both present a unimodal cell‐size distribution. At elevated temperatures, the generated crystalline superstructures including spherulites in the polymer matrix and transcrystals around the GF will cause a secondary heterogeneous cell nucleation. This leads to the observations of bimodal and trimodal cell‐size distributions in the pure PPS and the PPS/GF composites, respectively. The mechanisms for the solid‐state foaming behaviors of pure PPS and PPS/GF composites have been illustrated by establishing theoretical models. POLYM. COMPOS., 37:2527–2540, 2016. © 2015 Society of Plastics Engineers     

Fabrication,Thermoanalysis, and Performance Evaluation Studies on RDX‐based Microcellular Combustible Objects

In the development of weapons, the current trend is to replace incombustible constituent elements with combustible ones. The traditional porous combustible objects are composed of nitrocellulose as energetic component, which is highly sensitive and inflammable. Formulations composed of high content RDX and inert polymer binder were employed to replace the tradional ones. This paper reports the fabrication process of microcellular combustible objects with skin‐core structure using supercritical CO₂ (SC‐CO₂) as foaming agent. The objects were foamed in designed foaming molds with expansion ratios of 1.1, 1.2 and 1.35. The influence of foaming temperature, saturation pressure, expansion ratio and RDX content on porous structure was investigated by scanning electron microscopy (SEM). Thermogravimetric analysis was conducted and the results revealed a two‐stage decomposition process of RDX and binder. Performance in terms of heat resistance and moisture resistance was evaluated and compared with the traditional ones. A comparative study indicated that microcellular combustible objects are superior to traditional ones in respect of their survivability.     

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     

Preparation and morphology characterization of microcellular styrene‐co‐acrylonitrile (SAN) foam processed in supercritical CO2

Microcellular polymeric foam structures have been generated using a pressure‐induced phase separation in concentrated mixtures of supercritical CO₂ and styrene‐co‐acrylonitrile (SAN). The process typically generates a microcellular core structure encased by a non‐porous skin. Pore growth occurs through two mechanisms: diffusion of CO₂ from polymer‐rich regions into the pores and also through CO₂ gas expansion. The effects of saturation pressure, temperature and swelling time on the cell size, cell density and bulk density of the porous materials have been studied. Higher CO₂ pressures (hence, higher fluid density) provided more CO₂ molecules for foaming, generated lower interfacial tension and viscosity in the polymer matrix, and thus produced lower cell size but higher cell densities. This trend was similar to what was observed in swelling time series. While the average cell size increased with increasing temperature, the cell density decreased. The trend of bulk density was similar to that of cell size. © 2000 Society of Chemical Industry     

CO2‐Induced Mechanical Reinforcement of Polyolefin‐Based Nanocellular Foams

The effect of CO₂‐induced crystallization on the mechanical properties, in particular the yield and the ultimate stresses, of polyolefins is studied. PP and SEBS copolymer blends are used as examples and foamed after sorption of CO₂ at temperatures below T_m. CO₂ sorption thickens the crystalline lamellae and consequently increases T_m from 160 to 178 °C for both pure PP and PP/SEBS blend systems. Foams with an average cell size smaller than 250 nm retain the ultimate stress at the level of the polymer before foaming, even without the effect of CO₂‐induced crystallization. Including CO₂‐induced crystallization, the yield and the ultimate stresses of the foam can be improved by 30 and 50% over solid PP and by 22 and 40%, for solid PP/SEBS blends, respectively.

     

Effect of different experimental conditions on biodegradable polylactide membranes prepared with supercritical CO2 as nonsolvent

There is increasing interest in the application of supercritical CO₂ (SCCO₂) in the preparation of polymer membranes. Membrane formation with SCCO₂ as a nonsolvent is analogous to the conventional immersion precipitation process using an organic nonsolvent. Polylactide membranes were prepared with SCCO₂ as the nonsolvent under different experimental conditions such as different polymer concentrations, different depressurization rates, and different nonsolvent compositions. The effects of these conditions on the cross‐sectional structure were investigated through scanning electron microscopy. In addition, solvent‐induced crystallization and CO₂‐induced crystallization were studied. The crystallinity of PLA membranes prepared with different solvents or at different pressures was characterized by wide‐angle X‐ray diffraction and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 831–837, 2005     

Polycarbonate foams with tailor-made cellular structures by controlling the dissolution temperature in a two-step supercritical carbon dioxide foaming process

Closed-cell polycarbonate foams were prepared using a two-step foaming process, which consisted of the initial dissolution of supercritical CO₂ (scCO₂) into PC foaming precursors and their later expansion by heating using a double contact restriction method. The effects of the parameters of both CO₂ dissolution and heating stages on the cellular structure characteristics as well as on the physical aging of PC in the obtained foams were investigated. A higher amount of CO₂ was dissolved in PC with increasing the dissolution temperature from 80 to 100 °C, with similar CO₂ desorption trends and diffusion coefficients being found for both conditions. PC foams displayed an isotropic-like microcellular structure at a dissolution temperature of 80 °C. It was shown that it is possible to reduce their density while keeping their microcellular structure with increasing the heating time. On contrary, when dissolving CO₂ at 100 °C and later expanding, PC foams presented a cellular morphology with bigger cells and with an increasingly higher cell elongation in the vertical growth direction with increasing the heating time. Comparatively, PC foams obtained by dissolving CO₂ at 100 °C presented a more marked physical aging after CO₂ dissolution and foaming, although this effect could be reduced and ultimately suppressed with increasing the heating time.     

Investigation on the cell nucleation and cell growth in microcellular foaming by means of temperature quenching

The cell nucleation and real‐time cell growth with increasing cell growth time in microcellular foaming were investigated by means of temperature quenching in a supercritical CO₂ pressure‐quench process. Samples of uniform size and shape were saturated in a vessel under conditions of 100–180°C and 30 MPa, and then depressurized to the atmosphere in 10 s. After depressurization, these samples were removed from the vessel at prescribed intervals, and immediately immersed in an ice‐water slurry to obtain foamed samples with various cell growth times. It was found that the nucleation density is closely correlated to the gas absorption capacity of the polymer matrix, so that the final cell density should not be adopted as the nucleation density, as done commonly. The change of cell structure and mass density with increasing cell growth time was dominated by gas diffusion behavior, which was strongly influenced by the temperature. The final cell structure was mainly determined by the cell growth step, where gas diffusion played a key role. The final cell density was in direct proportion to the gas remaining in the substrate, which ranged from 6.0 × 10⁹ to 4.7 × 10⁶ cells/cm³. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 163–171, 2004     

Influence of fibrillated poly(tetrafluoroethylene) on microcellular foaming of polyamide 6 in the presence of supercritical CO2

In this article, PA6/poly(tetrafluoroethylene) (PTFE) composites were prepared by internal mixer with high rotor speed. The existence of PTFE nano-fibrillation network structure was observed by scanning electron microscopy (SEM) analysis. The effect of PTFE on crystallization and rheological behavior of PA6 was evaluated. The result showed that the PTFE fibrils improved the crystallization properties of PA6 and do not change the crystal structure. The PTFE effectively enhanced the melt strength of PA6 by fibrillation. The PA6/PTFE composites were then foamed assisted by supercritical CO₂. The PTFE was used as cell nucleating agent, crystal nucleating agent and melt strength enhancement agent in the foaming process. Finally, the microcellular PA6 foams were successfully obtained with the cell density higher than 10⁹ cells/cm³, the cell size of ca. 14 μm and the volume expansion ratio of 16.     

Microcellular and nanocellular solid-state polyetherimide (PEI) foams using sub-critical carbon dioxide I. Processing and structure

In this study we investigate the solid-state batch foaming of polyetherimide (PEI) using sub-critical CO₂ as a blowing agent. We report on the gas diffusion for various saturation pressures in this system. Foaming process characterization is reported detailing conditions used to create microcellular and nanocellular PEI foams of 40% and higher relative density. Gas sorption, foaming, and resultant morphologies are analyzed and compared to previously reported results on PEI thin films. It was found that equilibrium gas concentrations for PEI sheet begin to significantly exceed that of films for CO₂ pressures above 3 MPa. A large solid-state foaming process window has been identified that allows for the creation of either microcellular or nanocellular structures at comparable density reductions. A transition from micro-scale cells to nano-scale cells was observed at gas concentrations in the range of 94–110 mg CO₂/g PEI. Additionally, a hierarchical structure was observed which consisted of nanocellular structures internal to microcells. The PEI–CO₂ system offers the unique opportunity to compare and contrast the bulk properties of nanofoams and microfoams.     

Blending and foaming thermoplastic starch with poly (lactic acid) by CO2-aided hot melt extrusion

Biomaterials are materials that can be biodegradable or obtained from renewable resources. Among them, poly (lactic acid) (PLA) and thermoplastic starch (TPS) represent an interesting alternative to replace petro-sourced thermoplastics. In this study, blends made by TPS addition to PLA were subjected to a foaming process using supercritical CO₂-aided extrusion. Extruder die temperature and CO₂ content were the most prominent parameters explaining the structure of the foams obtained. Both parameters were intimately linked since the CO₂ flow depends on the melt temperature, the lower the temperature, the higher the CO₂ solubility. Therefore, the die temperature was chosen to pilot the process. Whatever the experimental conditions, a 50/50 (in wt%) blend was poorly foamed due to the strong incompatibility between both biopolymers. However, the blend made of 80 wt% PLA and 20 wt% TPS gave evenly foamed samples. In terms of expansion and type of porosity this blend behaved like pure PLA with high porosity, up to 96%, and the presence of a threshold die temperature separating a close cell porosity at lowest temperatures and an open cell structure above the threshold. This temperature threshold was however significantly lower to that obtained with pure PLA.     

Microcellular foaming of poly(phenylene sulfide)/poly(ether sulfones) blends using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide)/poly(ether sulfones) (PPS/PES) blends presents a promising approach to produce high‐performance cellular materials with tailored microstructures and enhanced properties. This study investigated the effects of multiphase blend composition and process conditions on the foaming behaviors and final cellular morphology, as well as the dynamic mechanical properties of the solid and microcellular foamed PPS/PES blends. The microcellular materials were prepared via a batch‐foam processing, using the environment‐friendly supercritical CO₂ (scCO₂) as a blowing agent. The saturation and desorption behaviors of CO₂ in PPS/PES blends for various blend ratios (10 : 0, 8 : 2, 6 : 4, 5 : 5, 4 : 6, 2 : 8, and 0 : 10) were also elaborately discussed. The experimental results indicated that the foaming behaviors of PPS/PES blends are closely related to the blend morphology, crystallinity, and the mass‐transfer rate of the CO₂ in each polymer phase. The mechanisms for the foaming behaviors of PPS/PES blends have been illustrated by establishing theoretical models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42634.     

Simple and feasible strategy to fabricate microcellular poly(butylene succinate) foams by chain extension and isothermal crystallization induction

In this article, a facile and efficient isothermal crystallization induction method was proposed to fabricate microcellular poly(butylene succinate) (PBS) foams with supercritical CO₂. The good regularity of PE chain segments and high reactive epoxy groups in ethylene-glycidyl methacrylate copolymer (PE-g-GMA) serving as a chain extender were employed to improve the crystallization behaviors, viscoelasticity, and foaming behaviors of PBS through chain extension reaction. The effect of PE-g-GMA content on the thermal properties, rheological performances, and cellular morphology of various PBS samples was investigated systematically. When the PE-g-GMA content switched from 7.5 to 10 wt %, an interesting transition from fine cells to microcells was observed in PBS/PE-g-GMA foams. Microcellular PBS foam modified by 10 wt % PE-g-GMA was successfully prepared at the foaming temperature of 87 °C and the induction time of 7 min, in which its cell size and cell density could reach 6.63 ± 1.93 μm and 3.75 × 10⁹ cells cm⁻³, respectively. The formation of abundant but tiny spherocrystals in chain extended PBS samples made a considerable contribution for preparing microcellular PBS foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48850.     

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.     

Effects of clay dispersion on the foam morphology of LDPE/clay nanocomposites

Intercalated and exfoliated low‐density polyethylene (LDPE)/clay nanocomposites were prepared by melt blending with and without a maleated polyethylene (PE‐g‐MAn) as the coupling agent. Their morphology was examined and confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of clay content and dispersion on the cell morphology of nanocomposite foams during extrusion foaming process were also thoroughly investigated, especially with a small amount of clay of 0.05–1.0 wt%. This research shows the optimum clay content for achieving microcellular PE/clay nanocomposite foams blown with supercritical CO₂. It is found that < 0.1 wt% of clay addition can produce the microcellular foam structure with a cell density of > 10⁹ cells/cm³ and a cell size of ～ 5 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2129–2134, 2007