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.     

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.     

Role of chain extension in the rheological properties,crystallization behaviors,and microcellular foaming performances of poly (butylene adipate-co-terephthalate)

Currently, the fabrication of microcellular semicrystalline polymer foam using supercritical CO₂ as a blowing agent constitutes a worldwide interest. In this work, a facile approach of chain extension and batch foaming was proposed to prepare microcellular semicrystalline poly (butylene adipate-co-terephthalate) (PBAT) foam using CO₂ as a physical blowing agent. With the introduction of chain extender (CE), the weight-average molecular weight and gel fraction of PBAT samples increased; their crystallization temperature increased from 74.2 to 86.9 °C and their viscoelasticity was improved greatly. Microcellular PBAT foams with the cell size <4 μm and the cell density more than 10¹⁰ cells cm⁻³ were fabricated successfully. With increasing concentration of CE, the cell density and volume expansion ratio (VER) of various PBAT foams increased from 3.4 × 10¹⁰ to 8.7 × 10¹⁰ cells cm⁻³ and from 1.5 to 2.0 times, respectively. With increasing foaming temperature, the cell size and VER increased and the cell density decreased. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47322.     

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%.     

Biopolymer foams from Novatein thermoplastic protein and poly(lactic acid)

A batch processing method is used to fabricate foams comprising of a blend of poly(lactic acid) (PLA) and Novatein, a protein‐based thermoplastic. Various compositions of Novatein/PLA are prepared with and without a compatibilizer, PLA grafted with itaconic anhydride (PLA‐g‐IA). Pure Novatein cannot form a cellular structure at a foaming temperature of 80 °C, however, in a blend with 50 wt % of PLA, microcells form with smaller cell sizes (3.36 µm) and higher cell density (8.44 × 10²¹ cells cm^?3) compared to pure PLA and blends with higher amounts of PLA. The incorporation of 50 wt % of semicrystalline Novatein stiffens the amorphous PLA phase, which restrains cell coalescence and cell collapse in the blends. At a foaming temperature of 140 °C, NTP₃₀–PLA₇₀ shows a unique interconnected porous morphology which can be attributed to the CO₂‐induced plasticization effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45561.     

Fabrication and cell morphology of a microcellular poly(ether imide)–carbon nanotube composite foam with a three-dimensional shape

The preparation of microcellular poly(ether imide) (PEI) based foams with three-dimensional geometry remains a great challenge worldwide. In this study, we fabricated microcellular PEI–carbon nanotube (CNT) bead foams with a batch rapid depressurization method in a self-designed mold with supercritical carbon dioxide (scCO₂) as a blowing agent. The effects of the saturation time, foaming temperature, foaming pressure, and depressurization rate on the microcellular structures of the PEI foam were analyzed by the Taguchi approach to determine the optimum foaming conditions, and the influence of the CNT content on the cell structure was analyzed. The results show that the depressurization rate and foaming temperature were the key factors influencing the cell size and cell density (N _f); that is, the high depressurization rate and low foaming temperature favored a small cell size and high N _f. The foaming temperature also influenced the foaming ratio (ϕ), and a high ϕ was obtained at a high foaming temperature. Under optimal foaming conditions, PEI with 2.0 wt % CNTs presented the best cell structure; N _f, cell size, and ϕ were 6.14 × 10¹⁰ cell/cm³, 2.43 μm, and 2.08, respectively. The mechanical properties of the final parts were related more to the foaming time and CNT concentration, and the maximum tensile and compression strength were reached at 3 h foaming time and 2.0 wt % CNT, that is, at 2.75 and 15.1 MPa (10% strain), respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47501.     

Solid‐state microcellular high temperature vulcanized (HTV) silicone rubber foam with carbon dioxide

A series of microcellular high temperature vulcanized (HTV) silicone rubber foams were prepared using CO₂ as a physical blowing agent. Rheological properties, gas diffusive behavior, and foaming parameters of silicone rubber were investigated. The results show that saturation pressure has a significant effect on the diffusivity of CO₂ in HTV silicone rubber matrix. The gas concentration and diffusivity increase from 2.45 wt % to 3.24 wt %, and from 1.62 × 10^?5 cm²/s to 7.83 × 10^?5 cm²/s as the saturation pressure increases from 2 MPa to 5 MPa, respectively. The value of the gas diffusivity in HTV silicone rubber is almost 1000 times higher than that of the gas diffusivity in polyetherimide (PEI) matrix. Additionally, microcellular HTV silicone rubber foams with the smallest cell diameter of 9.8 μm and cell density exceeding 10⁸ cells/cm³ are achieved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44807.     

Application of azodiisobutyronitrile and azobisisoheptonitrile in low‐density unsaturated polyester resin manufacturing

Low‐density unsaturated polyester resin (LDUPR) is an extended application of unsaturated polyester resin (UPR) material. In this study, azodiisobutyronitrile (AIBN) and azobisisoheptonitrile (ABVN) were presented as composite foaming agents and as initiators in LDUPR manufacturing. On the basis of the kinetics of AIBN and ABVN, their optimum half‐lives (t_1/2's) for LDUPR were both 1.0 h. In this study, the mass ratio of AIBN and ABVN was chosen at 7:3, and the preferred amount of the composite foaming agent was 2 wt % resin. They were treated at a molding temperature of 78.7 ± 1.0°C. The obtained LDUPR had an apparent density of 0.37 ± 0.01 g/cm³ and a specific compression strength of 35.58 ± 1.50 MPa·g^?1·cm^?3; it approached the highest specific compression strength value of rigid polyurethane foam (28–35 MPa g^?1 cm^?3). A dual‐initiation and dual‐foaming mechanism based on the dual‐exothermic decomposition properties of the composite foaming agent was proposed with the support of the differential scanning calorimetry and scanning electron microscopy results. In the first stage, ABVN decomposed, released bubble nuclei, and initiated UPR cross‐polymerization. The bubble nuclei spread in the resin glue and grew. In the second stage, the gas in resin glue was enriched by the AIBN decomposition. The gelation time of the resin glue was influenced by AIBN and delayed. With the curing of resin, more bubbles grew up, took shape, and were retained in the UPR matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40238.     

Formation of closed pore structure in CaO-MgO-Al2O3-SiO2 (CMAS) porous glass-ceramics via Fe2O3 modified foaming for thermal insulation

Due to the low density, low thermal conductivity and low water absorption, porous glass-ceramics have demonstrated excellent performance for thermal insulation. Closed pore structure can greatly reduce the thermal conductivity and convection as well as achieve high mechanical strength. However, yet it is difficult to realize closed pore structure due to the critical preparation condition. Here we use Fe₂O₃, which is the by-product of copper tailings, to optimize the pores structures of the porous glass-ceramics and facilitate the formation of uniform closed pore structure. The porous glass-ceramics were prepared by melting-quenching method, followed by sufficiently foaming through powder sintering route with SiC powders as foaming agent. The foaming process, micro structure, pore structure and thermal insulation performance were directly observed by heating microscope, scanning electron microscope (SEM), X-ray computed tomography and infrared thermal imager. The results show that the addition of Fe₂O₃ modified the depolymerization degree of the glass network and increased the numbers of non-bridged oxygen, decreasing the foaming temperature. The resultant closed pore structure showed a better thermal insulating performance than open pore structure. Accordingly, we achieved a low thermal conductivity of 0.19 W·m^?1·K^?1 with the highest specific strength of 19.55 MPa·g^?1·cm^?3 based on closed pore structure.     

Solid-state polyetherimide (PEI) nanofoams: the influence of the compatibility of nucleation agent on the cellular morphology

The introduction of polyhedral oligomeric silsesquioxane (POSS) particles which act as heterogeneous nucleation agent was applied to improve the cellular morphology of nanocellular polyetherimide (PEI) foams. The loading of POSS particles increases the solubility and diffusivity characteristics of gases in nanocomposite sheets by changing the distribution of the free volume and enlarging the unoccupied volume in polymer matrix. When the range of content of POSS particles is 0.2?~?1.0 wt. %, the range of the calculated surface tension of PEI/scCO₂ (γ _mix ) and radius of the critical nucleus (r*) are 30.98?~?28.14 mN/m, and 6.88?~?6.25 nm, respectively. However, the small aggregated POSS particles are favour of heterogeneous nucleation bacause the actual diameter of the aggregated POSS particles is approximate to twice r*, so the addtion of 0.5 wt. % POSS to PEI matrix presents excellent heterogeneous nucleation performance for foaming. The average cell size of 0.5 wt. % POSS/PEI nanofoams compared with neat PEI decreases from 108 to 66 nm and the cell density increses from 5.96?×?10¹⁴ to 3.34?×?10¹⁵ cells/cm³.     

The interaction of hydrogen sulfide with lead- and barium–cadmium–zinc-stabilized poly(vinyl chloride)

Poly(vinyl chloride) polymers stabilized with tribasic lead sulfate discolor upon exposure to hydrogen sulfide gas as a result of lead sulfide formation. The discoloration occurs for samples in both cord and sheet forms and is shown to be a function of total H₂S exposure, reaching a limiting value that is determined by the amount of lead stabilizer used in the polymer formulation. The permeation and diffusion constants for H₂S through PVC stabilized with tribasic lead sulfate and with a liquid Ba–Cd–Zn formulation are found to be P_Pb = (6.0 ± 0.2) × 10^?9, P_BaCdZn = (5.2 ± 0.2) × 10^?9 (both in cm³ gas?cm film/cm² area?sec?cm Hg), D_Pb = (1.3 ± 0.2) × 10^?7 cm²/sec, and D_BaCdZn = (6.4 ± 0.6) × 10^?8 cm²/sec, all measured at 21°C. The stabilizing efficiencies of the formulations were assessed by HCl evolution measurements, which show that exposure to H₂S decreases the initial polymer stability for both Pb-stabilized and Ba–Ca–Zn-stabilized formulations. Protection of stabilized PVC formulations from diffusing hydrogen sulfide is thus advisable for long-term stability as well as for color integrity.     

Controlling the structure of a porous polymer by coupling supercritical CO2 and single screw extrusion process

A study on the extrusion of Eudragit E100 was carried out using supercritical carbon dioxide (scCO₂) as plasticizer and foaming agent. ScCO₂ modifies the rheological properties of the material in the barrel of the extruder and acts as a blowing agent during the relaxation when flowing through the die. For experiments, a single‐screw extruder was modified to be able to inject scCO₂ within the extruded material. The aim is to determine a correlation between operating conditions and foam structure. The effect of three parameters was studied: the temperature in the die and in the metering zone, the screw speed, and the volumetric flow rate of CO₂. An increase in temperature enhances the expansion rate and the average pore diameter and appears to be the most significant parameter. The effect of CO₂ concentration is significant at small concentrations only: the higher the CO₂ concentration, the lower the pore density and the higher both the pore diameter and the expansion rate. The effect of the screw speed is tricky because a variation of this speed involves a decrease of CO₂ weight ratio. This study shows that the structure of the extrudates does not evolve with a coupling of screw speed increase and a subsequent CO₂ weight ratio decrease. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

Preparation of porous polyacrylamide hydrogels by frontal polymerization

Polyacrylamide hydrogels with defined porous structure were synthesized through frontal polymerization (FP) in the presence of NaHCO₃ as a foaming agent. Pore properties were analyzed using scanning electron microscopy and mercury intrusion porosimetry. The as‐prepared hydrogels displayed a small cell diameter of ca 2 µm. The dissolved foaming agent dispersing at the level of molecules and the polymerization front propagating step by step should be responsible for the small uniform cell structure. The pore volume varied from 0.63 to 3.65 cm³ g^?1 and the bulk density changed from 0.48 to 0.28 g cm^?3 for a foaming agent content from 0 to 18%. The hydrogels synthesized by FP exhibited higher swelling rate and swelling ratio with respect to conventional batch polymerization. The highest swelling ratio and rate were obtained at a foaming agent concentration of 12% based on monomer. Copyright © 2007 Society of Chemical Industry     

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.     

Phase appearance during polymerization of fluorinated polyimide monomers and deposition into the microscopic‐scale trenches in supercritical carbon dioxide

The phase appearance during the synthesis of fluorinated polyamic acid (PAA) from 2,2‐bis(3,4‐anhydrodicarboxyphenyl)‐hexafluoropropane (6FDA) and 2,2′‐bis(trifluoromethyl)?4,4′‐diaminobiphenyl (TFDB) in supercritical carbon dioxide (scCO₂) was investigated to obtain fundamental data for the deposition of fluorinate polyimides (PI) using scCO₂. All polymerizations were carried out at 30 MPa for 60 min. The experimental temperatures ranged from 50 to 70 °C, and each of the monomer concentrations ranged from 0.67 × 10^?5 to 3.3 × 10^?5 mol cm^?3. The holding time of the transparent phases, which was the time from the beginning of the polymerization to the appearance of a turbid phase, was increased with either a decrease in the polymerization temperature or a decrease in the initial monomer concentration. The holding time of the fluorinated PAA was longer than that of the monomers of Kapton‐type PAA. The deposition of PI into the microscopic‐scale trenches that had formed on the silicon wafer was successful in scCO₂. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43334.     

Lightweight polyethylene terephthalate bead foams with good interfacial adhesion and thermal insulation performance fabricated by supercritical carbon dioxide secondary foaming strategy

This paper reported the novel supercritical carbon dioxide (scCO₂) secondary foaming and molding strategy to prepare the thermal-insulation polyethylene terephthalate (PET) bead foam part with good interfacial adhesion and high expansion ratio. The incorporation of porous structure could effectively enhance the blowing agent solubility and fabricate the system viscosity difference, which contributed to the expansion and further welding of the expanded PET beads. Under the optimum foaming conditions, PET bead foam parts with excellent comprehensive performance were successfully prepared by molding method in the confined space via scCO₂ secondary foaming, and the corresponding welding mechanism of PET beads was further investigated. The obtained foam parts possessed good tensile and compressive properties, reaching 1.03 and 1.27 MPa (at 20% strain) respectively. Besides, the foam part exhibited the low thermal conductivity of 0.060 Wm⁻¹ K⁻¹, which confirmed the improvement of thermal insulation performance owing to the high expansion ratio.     

Porosity effect on microstructure,mechanical, and fluid dynamic properties of Ti2AlC by direct foaming and gel‐casting

In this study, Ti₂AlC foams were fabricated by direct foaming and gel‐casting using agarose as gelling agent. Slurry viscosity, determined by the agarose content (at a fixed solids loading), as well as surfactant concentration and foaming time were the key parameters employed for controlling the foaming yield, and hence the foam porosity after sintering process. Fabricated foams having total porosity in the 62.5‐84.4 vol% range were systematically characterized to determine their pore size and morphology. The effect of the foam porosity on the room‐temperature compression strength and elastic modulus was also determined. Depending on the amount of porosity, the compression strength and Young's modulus were found to be in the range of 9‐91 MPa and 7‐52 GPa, respectively. Permeability to air flow at temperatures up to 700°C was investigated. Darcian (k₁) and non‐Darcian (k₂) permeability coefficients displayed values in the range 0.30‐93.44 × 10^?11 m² and 0.39‐345.54 × 10^?7 m, respectively. The amount of porosity is therefore a very useful microstructural parameter for tuning the mechanical and fluid dynamic properties of Ti₂AlC foams.     

A Taguchi analysis on structural properties of polypropylene microcellular nanocomposite foams containing Fe2O3 nanoparticles in batch process

Polypropylene (PP) as a thermoplastic polymer has been foamed using batch foaming process. CO₂ is used as the blowing agent of the foaming. Ferrous oxide nanoparticles (nano Fe₂O₃) are also added as reinforcement. Effect of different parameters including nanoparticle weight percentage, foaming temperature and time on the structural properties of PP/nano Fe₂O₃ nanocomposites is investigated using Taguchi approach. Scanning electron microscope results depict that an appropriate microcellular structure is obtained with the cell density of 10⁹ cells/cm³ and almost 1 μm of cell size. Analysis of variance results indicated that foaming temperature is the most significant parameter on the structural properties. Cell density and expansion ratio are decreased by increasing foaming temperature. This phenomenon could be due to the reducing melt strength of polymer/gas mixture. It was also inferred that adding 2 wt% of nanoparticles leads to 80% improvement in cell density while cell size and expansion ratio was decreased.     

Effects of supercritical carbon dioxide treatment conditions on the gas separation properties of polydimethylsiloxane hybrid membrane materials for air purification

A siloxane/polydimethylsiloxane (PDMS) hybrid membrane containing fluorinated side chains was prepared by a convenient and mild sol–gel process and a crosslinking reaction. The effects of the supercritical carbon dioxide (scCO₂) conditions (i.e., treatment temperature, treatment time, and treatment pressure) on the permeation properties of fluorinated PDMS containing hybrid membrane were investigated. The chemical structure, microstructure, and physical performance of the membranes treated before and after were also discussed. The chemical structure of the PDMS membranes did not change with the scCO₂ treatment conditions. The membranes still retained better membrane‐forming abilities, higher permeability, and selectivity than normal PDMS membranes. Compared to those of the membrane with membrane formation after scCO₂ treatment, the oxygen permeability coefficient and oxygen/nitrogen separation factor of the membrane with scCO₂ treatment before membrane formation were higher and were up to 7.11 × 10^?8 cm³ (STP) cm/(cm² s cmHg) and 3.27, respectively. The permeation properties of the hybrid membrane were obviously higher than those of Robeson's upper bound. The high air‐purification performance of the hybrid membrane may have been due to the introduction of fluorine atoms into PDMS membrane, and the increase in free volume resulted from the plasticizing function of the scCO₂ treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013