Experimental study and thermodynamic model for respective solubilities of CO2 and ethanol for CO2‐ethanol‐polystyrene ternary system at elevated pressure and temperature

Foamed non‐Fickian diffusion (FNFD) model for a ternary system was proposed for the first time to regress the desorption data obtained by the gravimetric method. Results showed that FNFD model could accurately describe the diffusion behavior of CO₂ and ethanol out of foamed polystyrene (PS) and well predict total solubilities of CO₂ and ethanol in foamed PS. Meanwhile, Sanchez–Lacombe equation of state (S–L EoS) was adopted to calculate the respective solubilities (solubility of CO₂ in PS or solubility of ethanol in PS) and total solubilities of CO₂ and ethanol in PS for CO₂‐ethanol‐PS ternary system. Results showed that the total solubility of CO₂ and ethanol obtained from S–L EoS agreed well with values obtained by FNFD model. Furthermore, the respective and total solubilities of CO₂ and ethanol at 313.15, 338.15, and 343.15 K were calculated by S–L EoS. Results indicated that in the dissolving process, ethanol would be accelerated by CO₂ to dissolve into PS, and ethanol would compete with CO₂ to dissolve into PS, simultaneously. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46281.     

Investigation of the nanocellular foaming of polystyrene in supercritical CO2 by adding a CO2‐philic perfluorinated block copolymer

Nanocellular foaming of polystyrene (PS) and a polystyrene copolymer (PS‐b‐PFDA) with fluorinated block (1,1,2,2‐tetrahydroperfluorodecyl acrylate block, PFDA) was studied in supercritical CO₂ (scCO₂) via a one‐step foaming batch process. Atom Transfer Radical Polymerization (ATRP) was used to synthesize all the polymers. Neat PS and PS‐b‐PFDA copolymer samples were produced by extrusion and solid thick plaques were shaped in a hot‐press, and then subsequently foamed in a single‐step foaming process using scCO₂ to analyze the effect of the addition of the fluorinated block copolymer in the foaming behaviour of neat PS. Samples were saturated under high pressures of CO₂ (30 MPa) at low temperatures (e.g., 0°C) followed by a depressurization at a rate of 5 MPa/min. Foamed materials of neat PS and PS‐b‐PFDA copolymer were produced in the same conditions showing that the presence of high CO₂‐philic perfluoro blocks, in the form of submicrometric separated domains in the PS matrix, acts as nucleating agents during the foaming process. The preponderance of the fluorinated blocks in the foaming behavior is evidenced, leading to PS‐b‐PFDA nanocellular foams with cell sizes in the order of 100 nm, and bulk densities about 0.7 g/cm³. The use of fluorinated blocks improve drastically the foam morphology, leading to ultramicro cellular and possibly nanocellular foams with a great homogeneity of the porous structure directly related to the dispersion of highly CO₂‐philic fluorinated blocks in the PS matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Research on Preparation of Perfusion Explosive Using Foamed SF‐3 Double‐Base Propellant

Perfusion explosives were prepared using foamed SF‐3 propellants, which were synthesized by a two‐stage batch foaming process with different saturation time in supercritical fluid CO₂ as a foaming agent. The foamed SF‐3 propellants were characterized by scanning electron microscopy (SEM). Underwater detonation tests and test‐board detonation tests were carried out to investigate detonation performance of the prepared perfusion explosives. Results showed that more saturation time during the foaming process leads to more pores and cracks. Perfusion explosives prepared using foamed SF‐3 propellants exhibited much higher shock wave energy and stronger damage effectiveness than those using unfoamed SF‐3 propellants. Perfusion explosives prepared using foamed SF‐3 propellants with a saturation time of 2 h exhibited the highest shock wave energy and damage effectiveness, which decreased as the saturation time increased.     

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     

Cell structure and impact properties of foamed polystyrene in constrained conditions using supercritical carbon dioxide

To obtain cellular with small cell diameter, to control cell structure and to improve impact strength of foaming materials, the quick-heating method was applied for foaming polystyrene (PS) using supercritical CO₂ (Sc-CO₂) as physical blowing agent. Then, changes of cell structure and impact strength in microcellular foamed PS materials under constrained conditions were studied. The effects of foaming processing parameters, such as foaming temperature, saturation pressure and foaming time on the cell structure and impact strength of foamed PS in the constrained conditions were studied. The results showed that the Sc-CO₂ solubility and nucleation density in the constrained conditions were not influenced compared with those under free foaming conditions. However, cells in constrained foaming process are mostly circular and independent with thick cell walls; the phenomenon of cell coalescence and collapse was effectively eliminated under constrained conditions. In addition, cell diameters in constrained foaming process decrease with increase in foaming temperature and increase with increase in the foaming time. Compared with that in free foaming conditions, the cell growth was restrained dramatically under constrained conditions which resulted in smaller cell diameter. Moreover, higher impact strength could be obtained for foamed PS as foaming time was prolonged, foaming temperature was increased or saturation pressure was enhanced.     

CO2 foaming based on polystyrene/poly(methyl methacrylate) blend and nanoclay

A poly(methyl methacrylate) (PMMA) and nanoclay composite was dispersed into polystyrene (PS) using a twin‐screw extruder. The mixture was then batch foamed with supercritical CO₂. It was found that the cell density of foams based on the blend is higher than that based on the weight average of the two pure polymer components at the same foaming conditions. The cell size decreases and the cell density increases with the increase of the PMMA domain size. One explanation is that the large PMMA domains serve as a CO₂ reservoir and the nucleation in the PS phase is enhanced by the diffusion of CO₂ from the PMMA phase to the PS phase. Very small PMMA domains cannot function as a CO₂ reservoir, and so they are not able to facilitate the nucleation. A much higher cell density and smaller cell size were observed when nanoclay was located at the interface of the PMMA and the PS domains, serving as the heterogeneous nucleating agents. POLYM. ENG. SCI., 47:103–111, 2007. © 2007 Society of Plastics Engineers     

CO2 foaming of poly(ethylene glycol)/polystyrene blends: Relationship of the blend morphology,CO2 mass transfer,and cellular structure

When polymer blends are foamed by physical foaming agents, such as CO₂ or N₂, not only the morphology and viscosity of the blend polymers but also the solubility and diffusivity of the physical foaming agents in the polymers determine the cellular structure: closed cell or open cell and monomodal or bimodal. The foam of poly(ethylene glycol) (PEG)/polystyrene (PS) blends shows a unique bimodal (large and small) cellular structure, in which the large‐size cells embrace a PEG particle. Depending on the foaming condition, the average size of the large cells ranges from 40 to 500 μm, whereas that of small cells becomes less than 20 μm, which is smaller than that of neat PS foams. The formation mechanism of the cellular structure has been investigated from the viewpoint of the morphology and viscosity of the blend polymer and the mass‐transfer rate of the physical foaming agent in each polymer phase. The solubility and diffusivity of CO₂, which determine the mass‐transfer rate of CO₂ from the matrix to the bubbles, were measured by a gravimetric measurement, that is, a magnetic suspension balance. The solubility and diffusivity of CO₂ in PS differed from those in PEG: the diffusion coefficient of CO₂ in PEG at 110°C was 3.36 × 10^?9 m²/s, and that in PS was 2.38 × 10^?10 m²/s. Henry's constant in PEG was 5600 cm³ (STP)/(kg MPa) at 110°C, and that in PS was 3100 cm³ (STP)/(kg MPa). These differences in the transport properties, morphology of the blend, and CO₂‐induced viscosity depression are the control factors for creating the unique cellular structure in PEG/PS blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1899–1906, 2005     

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.     

Preparation and Characteristics of Foamed NC‐Based Propellants

Foaming properties of the three NC‐based (nitrocellulose‐based) propellants, namely, single‐base propellant, NG (nitroglycerine) propellant and TEGDN (triethylene glycol dinitrate) propellant were investigated in the batch foaming process by using supercritical CO₂ as the physical foaming agent. Burning characteristics of the foamed NC‐based propellants were also investigated in this work. For this study, the CO₂ desorption of the three NC‐based propellants were plotted by the gravimetric method. The morphology and burning characteristics of these foamed NC‐based propellants were characterized by scanning electron microscope (SEM) and closed vessel experiment. The test data revealed that the energetic plasticizer has a considerable effect on the pore formation in the NC matrix although it has little effect on the CO₂ solubility in the NC‐based propellants. Moreover, the SEM images showed the foaming temperature also plays an important role in the pore parameters of foamed propellants. Furthermore, the data of closed vessel experiment indicated that the burning characteristics of foamed NC‐based propellants largely depend on the pore parameters, and the porous structure of foamed propellants would considerably increase the mass conversion rate.     

(CO2 + 2‐propanol) mixture as a foaming agent for polystyrene: A simple thermodynamic model for the high pressure VLE‐phase diagrams taking into account the foam vitrification

The equation of state model developed by Lacombe and Sanchez (J Phys Chem 1976, 80, 2352) is used in the form proposed later by Sanchez and Stone (Polymer Blends, Vol. 1: Formulation, 2000; Chapter 2) to correlate experimental vapor‐liquid equilibrium (VLE) data for the three binaries and the ternary systems. Experimental data from the binary systems carbon dioxide‐isopropyl alcohol (CO₂‐IPrOH), isopropyl alcohol‐polystyrene (IPrOH‐PS), and carbon dioxide‐polystyrene (CO₂‐PS) are used to calculate VLE properties for the ternary system CO₂‐IPrOH‐PS. Two‐dimensional VLE‐phase diagrams were calculated and used to describe from a thermodynamic point of view the pressure, volume, and temperature values that characterize a thermoplastic foam evolution process, from the extruder to the foaming die. For different initial mixture CO₂ + IPrOH concentrations, pressure reduction produces liquid foaming until the vitrification curve arrests the final foam volume expansion. The dependence of the vitreous transition with the system CO₂ + IPrOH concentration while foaming is represented by the Chow (Macromolecules 1980, 13, 362) equation. The calculation procedure is proposed as a design tool to reduce the amount of experimental data usually needed as a requirement previous to the design stage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2663–2671, 2007     

CO2 removal by single and mixed amines in a hollow‐fiber membrane module—investigation of contactor performance

This work investigates CO₂ removal by single and blended amines in a hollow‐fiber membrane contactor (HFMC) under gas‐filled and partially liquid‐filled membrane pores conditions via a two‐scale, nonisothermal, steady‐state model accounting for CO₂ diffusion in gas‐filled pores, CO₂ and amines diffusion/reaction within liquid‐filled pores and CO₂ and amines diffusion/reaction in liquid boundary layer. Model predictions were compared with CO₂ absorption data under various experimental conditions. The model was used to analyze the effects of liquid and gas velocity, CO₂ partial pressure, single (primary, secondary, tertiary, and sterically hindered alkanolamines) and mixed amines solution type, membrane wetting, and cocurrent/countercurrent flow orientation on the HFMC performance. An insignificant difference between the absorption in cocurrent and countercurrent flow was observed in this study. The membrane wetting decreases significantly the performance of hollow‐fiber membrane module. The nonisothermal simulations reveal that the hollow‐fiber membrane module operation can be considered as nearly isothermal. © 2014 American Institute of Chemical Engineers AIChE J, 61: 955–971, 2015     

A novel thermoplastic polyurethane scaffold fabrication method based on injection foaming with water and supercritical carbon dioxide as coblowing agents

Injection foaming is an method for mass producing lightweight, foamed plastic components with excellent dimensional stability while using less material and energy. In this study, a novel injection foaming method employing supercritical CO₂ (scCO₂) and water as coblowing agents was developed to produce thermoplastic polyurethane (TPU) components with a uniform porous structure and no solid skin. Various characterization techniques were employed to investigate the cell morphology, crystallization behavior, and static and dynamic mechanical properties of solid injection molded samples, foamed samples using CO₂ or water as a single blowing agent, and foamed samples using both CO₂ and water as coblowing agents. When compared with CO₂ foamed samples, samples produced by the coblowing method exhibited much more uniform cell morphologies without a noticeable reduction in mechanical properties. Moreover, these TPU samples had almost no skin layer, which permitted the free transport of nutrients and waste throughout the samples. Such a mass‐produced, skin‐free structure is desirable in tissue engineering. In this study, the biocompatibility of the scaffolds was confirmed and the effect of these blowing agents on the TPU foaming behavior was studied. POLYM. ENG. SCI., 54:2947–2957, 2014. © 2014 Society of Plastics Engineers     

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.     

Elastomeric foam prepared by supercritical carbon dioxide

Biodegradable elastomer poly[(1,4‐butylene terephthalate)‐co‐(1,4‐butylene adipate)] foam was successfully prepared using supercritical CO₂. The elastomer foam has closed and uniform cell structure with density about 90 g/L. Narrow size distribution with average cell diameter 32 μm were obtained. The foamed balls show rubbery properties and can recover well (>90%) to their original shape quickly after releasing press stress. Cell growth needs to take place at melting state where the migration and orientation of polymer chains are permanently kept without remained force of springback. Some unique phenomena were observed during foaming the elastomer: post‐expansion (about 40%) was obtained after removing the foamed samples from a cylinder mold, which results in forming a ball rather than a cylinder like the mold. This phenomenon was explained by the lower glass transition temperature of the elastomer, in which residual CO₂ foam continuously in the room temperature; and “memory” of internal strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44354.     

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.     

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     

Solid‐state foaming of isotactic polypropylene and its composites with spherical or fibrous poly(butylenes terephthalate)

In this article, the foaming behavior of isotactic polypropylene (iPP) and its composites with spherical or fibrous poly(butylenes terephthalate) (PBT) using supercritical CO₂ as a blowing agent were investigated. Their foaming performances were also compared in relation to the crystal morphology and rheological behavior of PP. Results demonstrate that crystal structures significantly impacted the cell structures of foams. At relatively low temperature, microcells appeared at the centers of PP spherulites where the melting started. Particularly, bi‐modal cell structure formed in the foamed PP with increasing temperature. However, in the foamed PP composites with spherical or fibrous PBT, this structure almost disappeared due to the smaller PP spherulites. In foaming PP/PBT composites, the heterogeneous nucleation of spherical or fibrous PBT was effective at reducing cell size as well as improving cell density and cell uniformity. The fibrous PBT also acted as scaffolds for preserving cell shapes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41801.     

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.     

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     

Single and Binary CO2/CH4 Separation of a Zeolitic Imidazolate Framework‐8 Membrane

The performance of a zeolitic imidazolate framework‐8 (ZIF‐8) membrane in single and binary CO₂/CH₄ gas separation was investigated by means of a gas transport model that included generalized Maxwell‐Stefan and binary friction models. The model concerns gas diffusion through the membrane layer, gas flow through membrane intercrystalline pores, and resistance of the support layer. The effective membrane area considering the actual area for the gas permeated through the membrane was also introduced in this model. The selective ZIF‐8 membrane was successfully synthesized using a microwave‐assisted solvothermal method on an α‐alumina support pre‐attached with ZIF‐8 seeds by solvent evaporation. The simulated data agreed well with the experimental data. The model revealed that the membrane intercrystalline pores and its effective area significantly affected the CO₂/CH₄ gas permeation and separation performance.