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).     

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).     

Controlling the foam morphology of supercritical CO2-processed poly(methyl methacrylate) with CO2-philic hybrid nanoparticles

Highly CO₂-philic nanoparticles, octatrimethylsiloxy polyhedral oligomeric silsesquioxanes (POSS) are used to increase the affinity of poly(methyl methacrylate) (PMMA) to CO₂ in supercritical carbon dioxide (scCO₂) foaming, thus to improve its foaming performance and the foam morphology. PMMA and PMMA-POSS composite foams were produced based on the two-factorial design, at the upper and lower experimental conditions of pressure, temperature, processing time, and venting rate. The foams of PMMA-5% POSS composites exhibited smaller average pore sizes and higher pore densities than neat PMMA and PMMA-0.5% POSS composites. The smallest average pore diameter (0.3 μm) and the highest pore density (6.33 × 10¹² cm⁻³) were obtained with this composite processed at 35°C, 32 MPa, for 24 h and depressurized with fast-venting rate (0.4 MPa/s). ScCO₂ processing decreased the density of the polymer by more than 50%.     

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     

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.     

Synergy of supercritical CO2 and superheated H2O for enhanced processability of polyethersulfone towards open cell foams

Processing of a high glass transition (T_g) polymer such as polyethersulfone (PES; T_g = 225°C) poses a challenge as it requires high processing temperatures or sometimes toxic solvents. In this work, we report of a facile process using superheated water (shH₂O) and supercritical carbon dioxide (scCO₂) co‐media. PES solids were foamed in the scCO₂/shH₂O co‐media or scCO₂ alone in a batch process at different temperatures. The scCO₂/shH₂O produced a synergistic effect and achieved PES foams even at processing temperatures as low as 85°C below the nominal T_g; whereas, scCO₂ alone required higher processing temperatures. Moreover, the scCO₂/shH₂O co‐media produced highly porous PES foams that were at least 23% higher in porosity than what was obtained using scCO₂ alone. In addition, the scCO₂/shH₂O produced open cell foams at some processing conditions; whereas, scCO₂ produced closed cell morphologies. Since both CO₂ and H₂O are innocuous, this approach has potential for use in the preparation of ultrafiltration membranes, which currently require the use of toxic solvents for their fabrication by way of the phase inversion process. Moreover, the use of scCO₂/shH₂O is a cost‐effective approach for the processing of high T_g polymers at significantly lower temperatures. POLYM. ENG. SCI., 58:1108–1114, 2018. © 2017 Society of Plastics Engineers     

Control of micro‐ and nanocellular structures in CO2 foamed PES/PEN blends

High performance thermoplastic blends based on polyethersulfone (PES) and poly(ethylene 2,6 naphthalate) (PEN) were foamed with supercritical CO₂ to develop high‐performance foams with improved heat deflection temperature, extended processing range, and controlled cellular morphology. The cellular morphology resulted to be strongly influenced by the initial morphology of the blend. The presence of small amount of PES as dispersed phase in PEN based blends acted as blowing agent reservoir and allowed to extend the processing temperature range for obtaining low density foams. The presence of PEN droplets in PES based systems extended the foaming temperatures towards lower values and allowed the development of a bimodal micro/nanocellular morphology at a foaming temperature 60°C lower than the PES glass transition temperature. Furthermore, the presence of PEN droplets compensated for the reduced capability of the host matrix to generate a fine and diffuse porosity at low foaming temperatures. POLYM. ENG. SCI., 55:1281–1289, 2015. © 2015 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.     

Diffusion and desorption of CO2 in foamed polystyrene film

Based on the existence of the pores in foamed polystyrene (PS), foamed‐non‐Fickian diffusion (FNFD) model was proposed, for the first time, to regress the desorption data obtained by gravimetric method. Results showed that FNFD model could accurately describe the diffusion behavior of CO₂ out of foamed PS, and well predict the solubility of CO₂ in foamed PS. The characterization of scanning electron microscopy indicated that there were abundant pores in the foamed PS, and the pores store most of CO₂, which would diffuse in the pores, adsorb to the wall of the pores, penetrate across walls of the pores, diffuse in the matrix of PS, and desorb out of PS. The mass of CO₂ in the pores of foamed PS was expressed as a function of foaming pressure and temperature according to foaming kinetics. Results showed that the values calculated by this function agreed well with the values obtained from the FNFD model. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45645.     

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.     

Micro and nano cellular amorphous polymers (PMMA, PS) in supercritical CO2 assisted by nanostructured CO2-philic block copolymers - One step foaming process

Microcellular foaming of commodity amorphous polymers, poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) was studied in supercritical CO₂ via a batch one-step process in the presence of block copolymers able to change their foaming behaviour and therefore the porous structures. Triblock (styrene-co-butadiene-co-methylmethacrylate SBM, methylmethacrylate-co-butylacrylate-co-methylmethacrylate MAM) terpolymers were blended to PS or PMMA by extrusion. They showed advantages compared to classical PS-PMMA polymer blends in terms of cell size control and reduction of cell size. Foaming is carried out on bulk injection molded samples which were saturated under high pressures of CO₂ (300 bars) at different temperatures (25° C to 80 °C) and different depressurization rates (pressure drop rates from 150 bar/min to 12 bar/min). Very distinct cellular structures and densities were controlled by varying either the copolymer type or the foaming conditions (T,P). Cell sizes ranged from 0.2 μm to 200 μm, and densities from 0.30 g/cm³ to 1 g/cm³ in the polymers considered. Particularly, when triblock copolymers were able to self organize (nanostructuring) in a polymer matrix, they became phase separated at a nanometer level, presenting nanostructured polymers matrixes. To conclude the study, a possible nanostructuring mechanism is suggested based on the interplay between rubbery and highly CO₂-philic blocks/rigid and less CO₂-philic blocks. It is demonstrated that block copolymer additives are a good pathway towards micro and ultra microcellular supercritical CO₂ foaming of amorphous polymers.     

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.     

Fabrication of bimodal porous PLGA scaffolds by supercritical CO2 foaming/particle leaching technique

Specific pore structure is a vital essential for scaffolds applied in tissue engineering. In this article, poly(lactide‐co‐glycolide) (PLGA) scaffolds with a bimodal pore structure including macropores and micropores to facilitate nutrient transfer and cell adhesion were fabricated by combining supercritical CO₂ (scCO₂) foaming with particle leaching technique. Three kinds of NaCl particles with different scales (i.e., 100–250, <75, <10 μm) were used as porogens, respectively. In particular, heterogeneous nucleation occurred to modify scCO₂ foaming/particle leaching process when NaCl submicron particles (<10 μm) were used as porogens. The observation of PLGA scaffolds gave a formation of micropores (pore size <10 μm) in the cellular walls of macropores (pore size around 100–300 μm) to present a bimodal pore structure. With different mass fractions of NaCl introduced, the porosity of PLGA scaffolds ranged from 68.4 ± 1.4 to 88.7 ± 0.4% for three NaCl porogens. The results of SEM, EDS, and in vitro cytotoxicity test of PLGA scaffolds showed that they had uniform structures and were compatible for cell proliferation with no toxicity. This novel scCO₂ foaming/particle leaching method was promising in tissue engineering due to its ability to fabricate scaffolds with precise pore structure and high porosity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43644.     

Solid-state supercritical CO2 foaming of PCL and PCL-HA nano-composite: Effect of composition, thermal history and foaming process on foam pore structure

In this work we investigated the solid-state supercritical CO₂ (scCO₂) foaming of poly(?-caprolactone) (PCL), a semi-crystalline, biodegradable polyester, and PCL loaded with 5 wt% of hydroxyapatite (HA) nano-particles.In order to investigate the effect of the thermal history and eventual residue of the crystalline phase on the pore structure of the foams, samples were subjected to three different cooling protocols from the melt, and subsequently foamed by using scCO₂ as blowing agent. The foaming process was performed in the 37-40 °C temperature range, melting point of PCL being 60 °C. The saturation pressure, in the range from 10 to 20 MPa, and the foaming time, from 2 to 900 s, were modulated in order to control the final morphology, porosity and pore structure of the foams and, possibly, to amplify the original differences among the different samples.The results of this study demonstrated that by the scCO₂ foaming it was possible to produce PCL and PCL-HA foams with homogeneous morphologies at relatively low temperatures. Furthermore, by the appropriate combination of materials properties and foaming parameters, we prepared foams with porosities in the 55-85% range, mean pore size from 40 to 250 μm and pore density from 10⁵ to 10⁸ pore/cm³. Finally, we also proposed a two-step depressurization foaming process for the design of bi-modal and highly interconnected foams suitable as scaffolds for tissue engineering.     

Measurement and prediction of LDPE/CO2 solution viscosity

When CO₂ is dissolved into a polymer, the viscosity of the polymer is drastically reduced. In this paper, the melt viscosities of low‐density polyethylene (LDPE)/supercritical CO₂ solutions were measured with a capillary rheometer equipped at a foaming extruder, where CO₂ was injected into a middle of its barrel and dissolved into the molten LDPE. The viscosity measurements were performed by varying the content of CO₂ in the range of 0 to 5.0 wt% and temperature in the range of 150°C to 175°C, while monitoring the dissolved CO₂ concentration on‐line by Near Infrared spectroscopy. Pressures in the capillary tube were maintained higher than an equilibrium saturation pressure so as to prevent foaming in the tube and to realize single‐phase polymer/CO₂ solutions. By measuring the pressure drop and flow rate of polymer running through the tube, the melt viscosities were calculated. The experimental results indicated that the viscosity of LDPE/CO₂ solution was reduced to 30% of the neat polymer by dissolving CO₂ up to 5.0 wt% at temperature 150°C. A mathematical model was proposed to predict viscosity reduction owing to CO₂ dissolution. The model was developed by combining the Cross‐Carreau model with Doolittle's equation in terms of the free volume concept. With the Sanchez‐Lacombe equation of state and the solubility data measured by a magnetic suspension balance, the free volume fractions of LDPE/CO₂ solutions were calculated to accommodate the effects of temperature, pressure and CO₂ content. The developed model can successfully predict the viscosity of LDPE/CO₂ solutions from PVT data of the neat polymer and CO₂ solubility data.     

CO2‐switchable polymeric vesicle‐network structure transition induced by a hairpin‐line molecular configuration conversion

A triblock copolymer, containing a polyethylene glycol (PEG) block and two symmetrical poly(2‐(dimethylamino)ethyl methacrylate) (PDM) blocks, was synthesized by using PEG‐based macroinitiator with copper‐mediated living radical polymerization. The conductivity tests showed that the copolymer exhibited switchable responsiveness to CO₂, i.e., a relatively high conductivity of solution can be switched on and off by bubbling and removing of CO₂. According to the nuclear magnetic resonance results, the CO₂‐switchable conductivity variation could be attributed to protonation and deprotonation of tertiary amine groups in PDM blocks. Moreover, at a proper weight concentration 0.5%, the copolymer aqueous solution displayed a CO₂‐switchable viscosity variation. Scanning electron microscopy, cryogenic transmission electron microscopy, and dynamic light scattering characterization jointly demonstrated that the viscosity variation was the result of a CO₂‐switchable vesicle‐network aggregate structure transition. This structure transition can actually be attributed to a hairpin‐line molecular configuration conversion in terms of the reasonable mechanism discussion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44417.     

Measurement of interfacial tension in PS/LDPE melts saturated with supercritical CO2

The effect of supercritical carbon dioxide (scCO₂) on the interfacial tension between a polymer melt pair—polystyrene (PS) and low density polyethylene (LDPE)—was studied using the pendant drop method at temperatures varying from 200 to 240°C and CO₂ pressures up to 18 MPa. The LDPE melt was prepared in a high pressure optical cell and the PS pendant drop was injected into the LDPE melt with a special high pressure syringe. For measurements with scCO₂, the optical cell was first pressurized with scCO₂ and measurements were taken after the saturation of scCO₂ into both polymer melts. Excellent agreement was found with literature data for the same system without using scCO₂. For the polymer pair saturated with scCO₂, it was found that the interfacial tension decreases significantly with increasing CO₂ pressure and appears to level off at higher CO₂ pressures.     

Low‐temperature clean preparation of poly(lactic acid) foams by combining ethyl lactate and supercritical CO2: correlation between processing and foam pore structure

This study reports the low‐temperature and clean fabrication of porous poly(lactic acid) (PLA) through solid‐state foaming using various mixtures of ethyl lactate (EL) and supercritical CO₂ (scCO₂) as the blowing agent. Results showed that adding a small amount of EL (up to 0.2% molar fraction) to scCO₂ enhanced the plasticizing effect of the blowing agent mixture. As a direct consequence, at an operating temperature of 35 °C, PLA foams could be manufactured with homogeneous morphology, density as low as 0.09 ± 0.01 g cm^?3, mean pore sizes up to 519.0 ± 205.0 µm and pore densities in the range 2.0 × 10⁵ to 3.4 × 10⁸ pores cm^?3. Conversely, at a temperature of 40 °C, an increase of plasticizer concentration in the blowing agent mixture up to 0.2% promoted the crystallization of the polymer during sorption stage and, consequently, foaming was slightly reduced. © 2013 Society of Chemical Industry     

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