Synthesis and foaming of water expandable polystyrene-activated carbon (WEPSAC)

In this study, water acts as a co-blowing agent to support carbon dioxide (CO₂) in the extrusion foaming process of polystyrene (PS) to produce foams with very low density for thermal insulation applications. Herein, we report a simple suspension polymerization method to prepare water expandable polystyrene (WEPS) based on a PS/water containing activated carbon (AC) composite. AC pre-saturated with water was introduced into the styrene monomer to form a water-in-oil inverse emulsion without emulsifiers. Via suspension polymerization, water expandable PS/AC (WEPSAC) beads could be subsequently obtained. Low density PS foams (∼0.03 g/cc) were successfully produced in the CO₂ extrusion foaming process using WEPSAC. Because of lower foam density and better IR absorption due to the presence of water containing AC, WEPSAC foams provided a lower thermal conductivity than conventional talc reinforced PS foams.     

Introducing water as a coblowing agent in the carbon dioxide extrusion foaming process for polystyrene thermal insulation foams

In this study, water was used as a coblowing agent in the carbon dioxide (CO₂) extrusion foaming process in a twin screw extruder. It enlarged cell size and thus lowered foam density for better thermal insulation. Different strategies have been studied including direct injection of water into the extruder with surfactants, extrusion foaming of water expandable polystyrene (WEPS) beads, and feeding water containing activated carbon (WCAC)/polystyrene (PS) pellets. It was found that WCAC/PS pellets provided the most stable and clean extrusion process, more uniform cell morphology, and better thermal insulation than other methods. POLYM. ENG. SCI., 50:1577–1584, 2010. © 2010 Society of Plastics Engineers     

Fabrication of polystyrene/nano‐CaCO3 foams with unimodal or bimodal cell structure from extrusion foaming using supercritical carbon dioxide

The article surveyed the fabrication of polystyrene (PS)/nano‐CaCO₃ foams with unimodal or bimodal cellular morphology from extrusion foaming using supercritical carbon dioxide (sc‐CO₂). In order to discover the factors influenced the cell structure of PS/nano‐CaCO₃ foams, the effects of die temperature, die pressure, and nano‐CaCO₃ content on cell size, density, and morphology were investigated detailed. The results showed that the nano‐CaCO₃ content affected the cell size and morphology of PS/nano‐CaCO₃ foams significantly. When the die temperature and pressure was 150°C and 18 MPa, respectively, the foams with 5 wt% nano‐CaCO₃ exhibited the unimodal cellular morphology. As the nano‐CaCO₃ content increased to 20 wt%, a bimodal cell structure of the foams could be obtained. Moreover, it was found that the bimodal structure correlated more strongly with the pressure drop than the foaming temperature. The article revealed that unimodal or bimodal cellular morphology of PS/nano‐CaCO₃ foams could be achieved by changing the extrusion foaming parameters and nano‐CaCO₃ content. POLYM. COMPOS., 37:1864–1873, 2016. © 2015 Society of Plastics Engineers     

Extrusion foaming of polystyrene/carbon particles using carbon dioxide and water as co-blowing agents

Carbon particles such as platelet-like graphite (GR), spherically shaped activated carbon (AC), and tubular carbon nanofiber (CNF) were used as additives in extruded polystyrene (PS) foams with carbon dioxide (CO₂) and water as co-blowing agents. It was found that GR is the best additive for improving the thermal insulation performance of CO₂ based foam samples because of GR’s good absorption and reflectivity of infrared (IR) radiation. However, when the GR concentration was higher than 0.5 wt.%, the extruded foams exhibited large bubbles in the center of the foam and the extrusion line became unstable. By adding water carried by AC as a co-blowing agent, it was able to decrease the temperature in the center of the extruded foam, which successfully eliminated the bubble problem and achieved stable foam extrusion with good control of the foam density and cell morphology. Moreover, water carried by AC could also improve the mechanical performance of extruded foams containing CNF or GR. Water was not found in the extruded foams and the presence of water during extrusion did not affect the molecular weight and glass transition temperature of PS. Our results showed that a combination of AC as a water carrier and GR as an absorber and reflector of IR radiation can produce CO₂ based PS foams with good thermal insulation and mechanical properties, particularly with the presence of a small amount of CNF nanoparticles.     

The preparation and properties of polystyrene/functionalized graphene nanocomposite foams using supercritical carbon dioxide

In this work, polystyrene (PS)/functionalized graphene nanocomposite foams were prepared using supercritical carbon dioxide. Thermally reduced graphene oxide (TRG) and graphene oxide (GO) were incorporated into the PS. Subsequently, the nanocomposites were foamed with supercritical CO₂. The morphology and properties of the nanocomposites and the nucleation efficiency of functionalized graphene in foaming PS are discussed. Compared with GO, TRG exhibited a higher nucleation efficiency and more effective cell expansion inhibition thanks to its larger surface area and better exfoliated structure. It is suggested that the factors that have a significant influence on the nucleation efficiency of TRG and GO originate from the differences in surface properties and chemical structure. Furthermore, PS/TRG nanocomposites and their nanocomposite foams also possess good electrical properties which enable them to be used as lightweight functional materials.© 2012 Society of Chemical Industry     

Foaming behavior of isotactic polypropylene in supercritical CO2 influenced by phase morphology via chain grafting

Polystyrene (PS) and poly(methyl methacrylate) (PMMA) grafted isotactic polypropylene copolymers (iPP-g-PS and iPP-g-PMMA) with well-defined chain structure were synthesized by atom transfer radical polymerization using a branched iPP (iPP-B) as polymerization precursor. The branched and grafted iPP were foamed by using supercritical CO₂ as the blowing agent with a batch method. Compared to linear iPP foam, the iPP-B foams had well-defined close cell structure and increased cell density resulted from increased melt strength. Further incorporating PS and PMMA graft chains into iPP-B decreased the crystal size and increased the crystal density of grafted copolymers. In iPP-g-PS foaming, the enhanced heterogeneous nucleation by crystalline/amorphous interface further decreased the cell size, increased the cell density, and uniformized the cell size distribution. In contrast to this, the iPP-g-PMMA foams exhibited the poor cell morphology, i.e., large amount of unfoamed regions and just a few cells distributed among those unfoamed regions, although the crystal size and crystal density of iPP-g-PMMA were similar to those of iPP-g-PS. It was found that the iPP-g-PMMA exhibited PMMA-rich dispersed phase, which had higher CO₂ solubility and lower nucleation energy barrier than copolymer matrix did. The preferential cell nucleation within the PMMA-rich phase or at its interface with the matrix accounted for the poor cell morphology. The different effect of phase morphology on the foaming behavior of PS and PMMA grafted copolymers is discussed with the classical nucleation theory.     

Climate‐friendly polyurethane blowing agent based on a carbon dioxide adduct from palmitic acid grafted polyethyleneimine

To explore a new blowing agent for polyurethanes (PUs), palmitic acid was grafted onto a branched polyethyleneimine (bPEI; weight‐average molecular weight = 25,000 Da) via N,N′‐carbonyldiimidazole condensation to form a hydrophobically modified bPEI [palmitic acid grafted branched polyethyleneimine (C₁₆–bPEI)] with a grafting rate of 12%. A CO₂ adduct of C₁₆–bPEI, which trapped 16.8% CO₂ in it, was synthesized from C₁₆–bPEI. The long alkyl chain grafting improved the dispersibility of the CO₂ adduct in the PU raw materials and favored a homogeneous release of CO₂ to blow PUs during the exothermic foaming process. The preliminary results show that the foams possessed a density of 72.0 kg/m³ and a compressive strength of 246 kPa; this matched the required values of foams for the thermal insulation of underground steel pipes. This new blowing agent emitted nothing but CO₂ to the atmosphere, so it will not promote ozone depletion and will avoid global warming problems that are associated with traditional blowing agents such as chlorofluorocarbons and hydrochloroflourocarbons. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43874.     

Batch Foam Processing of Polypropylene/Polydimethylsiloxane Blends

Batch foaming processes were employed to prepare plastic foams from polypropylene (PP)/polydimethylsiloxane (PDMS) blends. Various amounts of PDMS were added to a PP matrix, and the resulting blends were batch foamed at different saturation pressures using carbon dioxide (CO₂) as the blowing agent. Ultimately, the blend foams exhibited better cell morphologies and higher cell densities in comparison with those prepared from PP alone. The increased solubility of CO₂ in PDMS made it as a CO₂ reservoir to induce more nucleation. When the PDMS content exceeded a certain level, however, it exerted a negative influence on cell density. Moreover, as the saturation pressure was raised, the cell density of the blend foams increased significantly. It was also noted that the addition of PDMS to the PP matrix generated some very small cells in the larger cell walls.     

Polyurethane foaming with CO2 adducts from C8 alkyl grafted polyethyleneimines: Optimization of the grafting rate and application of the blowing agents

We previously explored a series of CO₂ adducts from alkylated polyethylenimines with C₄ to C₁₆ alkyl side chains, serving as climate-friendly blowing agents for polyurethanes (PUs). Among them, the polyethylenimine with C₈ alkyl (2-ethylhexyl) side chains demonstrated the highest foaming efficiency. In this study, we further changed the grafting rate of the C₈ alkyl, from 7 to 16%, and investigated the effects of the resulting blowing agents on the foaming process. For both foaming systems containing a castor oil-derived polyol (Polycin T-400) or a poly(propylene glycol) polyol (Polyether 4110), the CO₂ adducts with a grafting rate of 13% displayed the best foaming performance in terms of high dispersibility in the foaming systems, homogenous cellular morphology, and good mechanical properties. Moreover, the 13%-C₈-alkylated blowing agent demonstrated high suitability for the foaming systems from biomass-sourced polyols (like Polycin T-400). Therefore, the optimized CO₂-adduct blowing agent could replace the currently used climate-changing hydrochlorofluorocarbons and hydrofluorocarbons, as well as might contribute to the development of future renewable PU foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48752.     

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     

Generation of low‐density high‐performance poly(arylene ether sulfone) foams using a benign processing technique

In this study, a benign process was used to successfully produce low density foam from poly(arylene ether sulfone) (PAES). Both carbon dioxide (CO₂) and water as well as nitrogen and water were used as physical blowing agents in a one‐step batch process. A large amount of blowing agents (up to 7.5%) was able to diffuse into the PAES resin in a 2‐h saturation time. Utilizing water and CO₂ as the blowing agents yielded foam with better properties than nitrogen and water because both the water and CO₂ are plasticizers for the PAES resin. PAES foam produced from CO₂ and water had a large reduction in foam density (～80%) and a cell size of ～50 μm, while maintaining a primarily closed cell structure. The small cell size and closed cell structure enhanced the mechanical properties of the foam when compared with the PAES foam produced from nitrogen and water. The tensile, compressive, and notched izod impact properties of the PAES foams were examined, and the compressive properties were compared to commercially available structural foams. With reduced compression strength of 39 MPa and reduced compression modulus of 913 MPa, the PAES foam is comparable to polyetherimide and poly(vinylchloride) structural foams. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

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     

Novel poly(aryl ether nitrile ketone) foams and the influence of copolymer structure on the foaming result

Novel poly(aryl ether nitrile ketone) foams were prepared through the batch foaming method with supercritical CO₂ as the blowing agent. Both temperature‐induced and pressure‐induced foaming methods were conducted to examine the influence of nitrile groups on the foaming result. The results indicated that nitrile groups influenced the foaming result by affecting both the viscoelasticity and CO₂ absorption of the polymers. In addition, the CO₂ solubility of the polymers increased with increasing CN content presumably because of the Lewis acid–base nature of the interaction between the CO₂ molecules and the nitrile groups. The cell growth process was assessed by analyzing the influence of foaming temperature and foaming time on the cell morphology. Nanocellular foams with a minimum size of 30–50 nm were achieved by the temperature‐induced foaming method. Moreover, highly expanded foams with a maximum expansion ratio of 23.6 were obtained by the pressure‐induced foaming method. © 2018 Society of Chemical Industry     

The synergy of supercritical CO2 and supercritical N2 in foaming of polystyrene for cell nucleation

This study examines the foaming behaviour of polystyrene (PS) blown with supercritical CO₂–N₂ blends. This is achieved by observing their foaming processes in situ using a visualization system within a high-temperature/high-pressure view-cell. Through analyzing the cell nucleation and growth processes, the foaming mechanisms of PS blown with supercritical CO₂–N₂ blends have been studied. It was observed that the 75% CO₂–25% N₂ blend yielded the highest cell densities over a wide processing temperature window, which indicates the high nucleating power of supercritical N₂ and the high foam expanding ability of supercritical CO₂ would produce synergistic effects with that ratio in batch foaming. Also, the presence of supercritical CO₂ increased the solubility of supercritical N₂ in PS, so the concentration of dissolved supercritical N₂ was higher than the prediction by the simple mixing rule. The additional supercritical N₂ further increased the cell nucleation performance. These results provide valuable directions to identify the optimal supercritical CO₂–N₂ composition for the foaming of PS to replace the hazardous blowing agents which are commonly used despite their high flammability or ozone depleting characteristics.     

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     

Effect of dispersion method and process variables on the properties of supercritical CO2 foamed polystyrene/graphite nanocomposite foam

In this study, polystyrene/nanographite nanocomposite foams were made by different compounding methods, such as direct compounding, pulverized sonication compounding, and in situ polymerization, to understand the effect of the process variables on the morphology of the nanocomposites and their foam. The foam was made by batch foaming using CO₂ as the blowing agent. Various foaming pressures and temperatures were studied. The results indicated that the cell size decreased and the cell morphology was improved with the advanced dispersion of the nanoparticles. Among the three methods, the in situ polymerization method provided the best dispersion and the resulting nanocomposite foam had the finest cell size and the highest cell density. In addition, adding nanoparticles as a nucleating agent can make foams of similar cell size and cell density at a much lower foaming pressure. This result can be explained by the classical nucleation theory. This discovery could open up a newroute to produce microcellular foams at a low foaming pressure. POLYM. ENG. SCI., 53:2061–2072, 2013. © 2013 Society of Plastics Engineers     

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.     

轻质环氧树脂微孔发泡材料的力学及隔热性能

通过添加不同含量的化学发泡剂,制备了较小密度(0.5 g/cm~3)的环氧树脂基微孔发泡材料,研究了发泡剂含量(0.25%~2%)对环氧复合发泡材料发泡行为的影响,并讨论了材料的力学性能及隔热性能的变化规律。结果表明,随着发泡剂含量的增加,材料的表观密度不断降低,但泡孔尺寸不断增大,泡孔密度则不断降低。力学性能及隔热性能测试表明,随发泡剂含量的增加,材料的压缩屈服强度和压缩弹性模量不断降低,但是材料的隔热性能不断提高。     

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     

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