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     

Synthesis and foaming of water expandable polystyrene-clay nanocomposites

The typical process used to synthesize water expandable polystyrene (WEPS) was modified and applied to prepare water expandable polystyrene (PS)-clay nanocomposites (WEPSCN). The natural clay can be uniformly dispersed in water due to its hydrophilicity. It can be further carried into the styrene monomer by the formation of water-in-oil inverse emulsion. Via suspension polymerization, spherical PS beads with myriads of water/clay droplets inside were obtained. Upon heating via the hot medium, the PS matrix was expanded to form a cellular structure. Transmission electron microscopy results indicated that nanoclay forms a layer around the cell wall. The presence of nanoclay led to higher water content in the beads and reduced the water loss during storage.Using CO₂ as the co-blowing agent, foams with a bi-model structure and lower densities were obtained. Furthermore, CO₂ foaming offers an alternative method to utilize dried WEPS/WEPSCN beads. The presence of water cavities significantly enlarges the cell size and leads to a foam product with ultra-low density (∼0.03 g/cc) and low thermal conductivity.     

Extruded polystyrene foams with bimodal cell morphology

Extrusion foaming using supercritical carbon dioxide (CO₂) as the blowing agent is an economically and environmentally benign process. However, it is difficult to control the foam morphology and maintain its high thermal insulation comparing to the conventional foams based on fluorocarbon blowing agents. In this study, we demonstrated that polystyrene (PS) foams with the bimodal cell morphology can be produced in the extrusion foaming process using CO₂ and water as co-blowing agents and two particulate additives as nucleation agents. One particulate is able to decrease the water foaming time so both CO₂ and water can induce foaming simultaneously, while the other increases the CO₂ nucleation rate with little effect on the CO₂ foaming time. Our experimental results showed that a dual particulate combination of nanoclay and activated carbon provided the best bimodal structure. The bimodal foams exhibited much better compressive properties and slightly better thermal insulation for PS foams.     

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.     

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 of polystyrene nanocomposite foams with supercritical CO2

Intercalated and exfoliated polystyrene/nano‐clay composites were prepared by mechanical blending and in situ polymerization respectively. The composites were then foamed by using CO₂ as the foaming agent in an extrusion foaming process. The resulting foam structure is compared with that of pure polystyrene and polystyrene/talc composite. At a screw rotation speed of 10 rpm and a die temperature of 200°C, the addition of a small amount (i.e., 5 wt%) of intercalated nano‐clay greatly reduces cell size from 25.3 to 11.1 μm and increases cell density from 2.7 × 10⁷ to 2.8 × 10⁸ cells/cm³. Once exfoliated, the nanocomposite exhibits the highest cell density (1.5 × 10⁹ cells/cm³) and smallest cell size (4.9 μm) at the same particle concentration. Compared with polystyrene foams, the nanocomposite foams exhibit higher tensile modulus, improved fire retardance, and better barrier property. Combining nanocomposites and the extrusion foaming process provides a new technique for the design and control of cell structure in microcellular foams.     

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     

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     

Effect of die temperature on the morphology of microcellular foams

A study on the extrusion of microcellular polystyrene foams at different foaming temperatures was carried out using CO₂ as the foaming agent. The contraction flow in the extrusion die was simulated with FLUENT computational fluid dynamics code at two temperatures (150°C and 175°C) to predict pressure and temperature profiles in the die. The location of nucleation onset was determined based on the pressure profile and equilibrium solubility. The relative importance of pressure and temperature in determining the nucleation rate was compared using calculations based on classical homogeneous nucleation theory. Experimentally, the effects of die temperature (i.e., the foaming temperature) on the pressure profile in the die, cell size, cell density, and cell morphology were investigated at different screw rotation speeds (10 ～ 30 rpm). Experimental results were compared with simulations to gain insight into the foaming process. Although the foaming temperature was found to be less significant than the pressure drop or the pressure drop rate in deciding the cell size and cell density, it affects the cell morphology dramatically. Open and closed cell structures can be generated by changing the foaming temperature. Microcellular foams of PS (with cell sizes smaller than 10 μm and cell densities greater than 10 cells/cm³) are created experimentally when the die temperature is 160°C, the pressure drop through the die is greater than 16 MPa, and the pressure drop rate is higher than 10⁹ Pa/sec.     

超临界CO_2发泡聚苯乙烯工艺研究

以超临界CO_2为发泡剂,采用釜压法在不同发泡工艺条件下制备了聚苯乙烯(PS)发泡试样,通过扫描电子显微镜对PS发泡试样的泡孔形貌进行了表征,探讨了不同发泡工艺对PS发泡试样发泡性能的影响。结果表明,随发泡温度的升高,PS发泡试样泡孔尺寸增大,泡孔密度下降,而泡沫密度呈现先降低后升高的趋势,发泡倍率与此相反;增大保压时间和保压压力,可提高试样的发泡效果。当发泡温度为136℃,保压压力为20 MPa,保压时间为4 h时,PS发泡试样的发泡效果最好,其泡沫密度为0.043 g/cm~3,发泡倍率为24.4,泡孔尺寸为59.8μm,泡孔密度为6.20×107个/cm~3。     

Preparation of halogen-free flame-retardant expandable polystyrene foam by suspension polymerization

In this research, using hexaphenoxycyclotriphosphazene (HPCTP) as the halogen-free flame retardant, we prepared flame-retardant expandable polystyrene (EPS) beads by suspension polymerization. The effects of process parameters and the amount of flame retardant on polystyrene (PS)/HPCTP composite beads were investigated. The results show that the change in HPCTP content has little effect on the particle size distribution of composite beads. When the oil–water ratio is 1/4, TCP dosage is 3 wt %, stirring rate is 350 rpm, initiator dosage is 1.25 wt %, and HPCTP dosage is 15 wt %, the size of the composite beads is uniform, and the average particle size is 1.12 mm. HPCTP formed nanodispersed particles in the PS matrix with an average particle size of 44.86 nm. In addition, the thermogravimetric behavior and heat-release properties of composite beads were evaluated. The results showed that HPCTP mainly acted in the gaseous phase, which can effectively decrease the maximum mass-loss rate of the PS/HPTCP composite beads and significantly reduce the heat-release rate and heat-release capacity. The EPS foams were obtained by a prefoaming method. The average cell diameter was 62.15 μm, and the foaming ratio was 11 times. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47779.     

Polypropylene‐dispersed domain as potential nucleating agent in PS and PMMA solid‐state foaming

The potential of using dispersive domains in a polymer blend as a bubble nucleating agent was investigated by exploiting its high dispersibility in a matrix polymer in the molten state and its immiscibility in the solid state. In this experiments, polypropylene (PP) was used as the nucleating agent in polystyrene (PS) and poly(methyl methacrylate) (PMMA) foams at the weight fraction of 10, 20, and 30 wt %. PP creates highly dispersed domains in PS and PMMA matrices during the extrusion processing. The high diffusivity of the physical foaming agent, i.e., CO₂ in PP, and the high interfacial tension of PP with PS and PMMA could be beneficial for providing preferential bubble nucleation sites. The experimental results of the pressure quench solid‐state foaming of PS/PP and PMMA/PP blends verified that the dispersed PP could successfully increase the cell density over 10⁶ cells/cm³ for PS/PP and 10⁷ cells/cm³ for PMMA/PP blend and reduce the cell size to 24 μm for PS/PP and 9 μm for PMMA/PP blends foams. The higher interfacial tension between PP and the matrix polymer created a unique cell morphology where dispersed PP particles were trapped inside cells in the foam. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Physical extruder foaming of poly(lactic acid)—processing and foam properties

The article describes extrusion foaming of poly(lactic acid) (PLA) using carbon dioxide in the supercritical state as foaming agent emphasizing the steps required to establish a stable extrusion process. Low melt strength of PLA plays a role in optimizing processing conditions. The tests included PLA grades of different viscosity in addition to a chain extender. Processing at low temperature is possible due to the plasticizing effect of the CO₂ on the PLA melt and a sufficiently low melt temperature is also a prerequisite in production of stable foams due to improved melt strength. Foams were characterized by density, cell structure, crystallinity, and mechanical properties in compression. Low density, microcellular foams with density down to 20–30 kg/m³ were obtained for three different PLA grades. Varying die temperature and pressure drop rate we can explain observed abrupt drops in density with increasing CO₂ content by the interplay between cell nucleation and gas diffusivity at given temperatures. An effect on melt strength similar to using a chain extender is achieved by lowering the melt temperature at the die. Observed variations in sample crystallinity do not correlate with foam density. The PLA foams have good energy absorption capability. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Preparation of polystyrene/montmorillonite nanocomposites in supercritical carbon dioxide

The preparation of polystyrene (PS)/montmorillonite (MMT) composites in supercritical carbon dioxide (SC? CO₂) was studied. Lipophilic organically modified MMT can be produced through an ion‐exchange reaction between native hydrophilic MMT and an intercalating agent (alkyl ammonium). PS/clay composites were prepared by free‐radical precipitation polymerization of styrene containing dispersed clay. X‐ray diffraction and transmission electron microscopy indicated that intercalation of MMT was achieved. PS/clay composites have a higher thermal decomposition temperature and lower glass‐transition temperature than pure PS. The IR spectrum analysis showed that the solvent of SC? CO₂ did not change the structures of the PS molecules, but there were some chemical interactions between the PS and the clay in the composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 22–28, 2005     

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.     

Rheology and extrusion foaming of chain‐branched poly(lactic acid)

In this study, the effect of macromolecular chain‐branching on poly(lactic acid) (PLA) rheology, crystallization, and extrusion foaming was investigated. Two PLA grades, an amorphous and a semi‐crystalline one, were branched using a multifunctional styrene‐acrylic‐epoxy copolymer. The branching of PLA and its foaming were achieved in one‐step extrusion process. Carbon dioxide (CO₂), in concentration up to 9%, was used as expansion agent to obtain foams from the two PLA branched using chain‐extender contents up to 2%. The foams were investigated with respect to their shear and elongational behavior, crystallinity, morphology, and density. The addition of the chain‐extender led to an increase in complex viscosity, elasticity, elongational viscosity, and in the manifestation of the strain‐hardening phenomena. Low‐density foams were obtained at 5–9% CO₂ for semi‐crystalline PLA and only at 9% CO₂ in the case of the amorphous PLA. Differences in foaming behavior were attributed to crystallites formation during the foaming process. The rheological and structural changes associated with PLA chain‐extension lowered the achieved crystallinity but slightly improved the foamability at low CO₂ content. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

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     

Experimental investigation on the role of PVA in eliminating inhibition phenomenon of carbon black during the synthesis of polystyrene/carbon black composite particles

In this study, the role of polyvinyl alcohol (PVA) in eliminating the inhibition phenomenon of modified light‐weight carbon black (CB) during the synthesis of polystyrene/modified light‐weight carbon black (PS/MLCB) composite particles was examined. It was interesting to note that the polymerization time was largely shortened in the presence of a certain PVA. And the effect of PVA dosage on the polymerization time and the macromorphology of obtained PS/MLCB composite particles were systematically investigated, as well as the correlation between PVA dosage, polymerization time, and MLCB content. In addition, the potential mechanism about the role of PVA in eliminating the inhibition phenomenon of MLCB during the suspension polymerization of styrene was also proposed and analyzed in detail. The PS/MLCB composites particles were studied in terms of surface morphology, thermal stability, and molecular weight. Scanning electron microscopy images of the resulting PS/MLCB composite particles demonstrated that CB was well dispersed in the PS matrix. And the thermal stability of obtained PS/MLCB composite particles was significantly enhanced with the incorporation of MLCB, and increased with the increasing content of MLCB. This synthesis technique brought about a promising future in the large‐scale production of black expandable polystyrene. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Mesoporous silica particles grafted with polystyrene brushes as a nucleation agent for polystyrene supercritical carbon dioxide foaming

In this study, spherical ordered mesoporous silica (s‐OMS) was applied as a new type of nucleating agent in polystyrene (PS) foaming with supercritical CO₂ as a blowing agent. These s‐OMS particles were modified by the selective grafting of PS brushes on the outside surface, by which the mesoporous structure inside particles could be maintained. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller surface area analysis were used to characterize the structure of the original and modified particles; these indicated that the PS brushes were grafted on the outside surface and the inside porous structure were maintained. PS/s‐OMS–PS composites were prepared by a solution blending method, and the s‐OMS–PS particles could have been well dispersed in the PS matrix because of the surface modification. Subsequently, PS and composite microcellular foams were prepared by a batch foaming process, and the morphology characterization on these foams showed that the s‐OMS particles exhibited an excellent heterogeneous effect on PS foaming. The heterogeneous effect became more significant when the foaming temperature or saturation pressure was low. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4308–4317, 2013     

Effects of styrene oligomers and polymers on the suspension polymerization behavior and properties of expandable polystyrene

Styrene oligomers are formed by a free‐radical mechanism during the thermal polymerization of styrene in storage. The effects of these compounds on the preparation of expandable polystyrene (EPS) were investigated with respect to suspension polymerization behavior and the properties of the impregnated polystyrene beads produced. Styrene dimers and trimers up to concentrations of 0.2 wt % did not affect the stability of the suspension during the polymerization and impregnation stages. Besides differentiated effects on the particle size distributions of the polymers and on the polymerization rate, no chain‐transfer activity of the oligomers was observed, and this confirmed the assignment of chain transfer to the Diels–Alder dimer in the literature. The investigation of the foaming behavior of the pentane‐impregnated EPS beads indicated a significant reduction of the prefoaming density caused by styrene dimers and trimers. This behavior resulted from a decrease in the glass‐transition temperatures of these polymers. The effects of high‐molecular‐weight polystyrene, formed in addition to oligomers during storage by the thermal polymerization of styrene, on the polymerization behavior and polymer properties of EPS were also investigated. The results showed a significant impact on the suspension stability that was dependent on the concentration of the high‐molecular‐weight polystyrene. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008