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     

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.     

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

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

The effect of pressurized carbon dioxide as a plasticizer and foaming agent on the hot melt extrusion process and extrudate properties of pharmaceutical polymers

The aim of the current research project was to explore the possibilities of combining pressurized carbon dioxide with hot melt extrusion of polyvinylpyrrolidone-co-vinyl acetate 64, Eudragit^® E100 and ethylcellulose 20 cps, to evaluate the ability of the pressurized gas to act as a temporary plasticizer as well as to produce a foamed polymeric material. Pressurized carbon dioxide was injected into a Leistritz Micro 18 intermeshing co-rotating twin-screw melt extruder using an ISCO 260D syringe pump. The physicochemical characteristics of the polymers before and after injection of carbon dioxide were evaluated using MDSC, dissolution measurements, specific surface area measurements, porosity, dynamic vapour sorption and microscopy. An extruder set up and screw configuration were configured and optimized for injection of pressurized CO₂. Carbon dioxide acted as plasticizer for all three polymers, reducing the processing temperature during the hot melt extrusion process. The specific surface area and the porosity of the polymers was increased after treatment with carbon dioxide, resulting in enhanced dissolution. The macroscopic morphology was changed to a foam-like structure due to expansion of the carbon dioxide at the extrusion die. This resulted in improved milling efficiency.     

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.     

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     

Ultrahigh compressive strength and heat resistance of polystyrene/polyphenylene oxide foams of supercritical carbon dioxide foaming

Polystyrene (PS) foam materials are lightweight, but suffer from poor compressive strength and heat resistance, among other problems, which limit their application. Herein, a method for preparing PS foam with high compressive strength and high heat resistance using supercritical CO₂ is proposed. PS/polyphenylene oxide (PPO) blends were prepared using a corotating intermeshing twin-screw extruder. The results showed that PPO exhibited excellent molecular-level compatibility with PS, which substantially improved mechanical properties and heat resistance of PS. Foam samples of PS/PPO blends with the same expansion ratio were prepared via batch foaming experiments, and the compressive strength of different foams was determined at different temperatures. At room temperature, the compressive strength of the PS/PPO-30% foam increased by 173% compared with pure PS foam. As the testing temperature increased from 30 to 120°C, the compressive strength of pure PS foams decreased rapidly. Nevertheless, PS/PPO foams maintained high compressive strength at high temperatures.     

Polycarbonate foams with tailor-made cellular structures by controlling the dissolution temperature in a two-step supercritical carbon dioxide foaming process

Closed-cell polycarbonate foams were prepared using a two-step foaming process, which consisted of the initial dissolution of supercritical CO₂ (scCO₂) into PC foaming precursors and their later expansion by heating using a double contact restriction method. The effects of the parameters of both CO₂ dissolution and heating stages on the cellular structure characteristics as well as on the physical aging of PC in the obtained foams were investigated. A higher amount of CO₂ was dissolved in PC with increasing the dissolution temperature from 80 to 100 °C, with similar CO₂ desorption trends and diffusion coefficients being found for both conditions. PC foams displayed an isotropic-like microcellular structure at a dissolution temperature of 80 °C. It was shown that it is possible to reduce their density while keeping their microcellular structure with increasing the heating time. On contrary, when dissolving CO₂ at 100 °C and later expanding, PC foams presented a cellular morphology with bigger cells and with an increasingly higher cell elongation in the vertical growth direction with increasing the heating time. Comparatively, PC foams obtained by dissolving CO₂ at 100 °C presented a more marked physical aging after CO₂ dissolution and foaming, although this effect could be reduced and ultimately suppressed with increasing the heating time.     

Compressive behavior of microcellular polystyrene foams processed in supercritical carbon dioxide

Microcellular polystyrene foams have been prepared using supercritical carbon dioxide as the foaming agent. The cellular structures resulting from this process have been shown to have a significant effect on the corresponding mechanical properties of the foams. Compression tests were performed on highly expanded foams having oriented, anisotropic cells. For these materials an anisotropic foam model can be used to predict the effect of cell size and shape on the compressive yield stress. Beyond yield, the foams deformed heterogeneously under a constant stress. Microstructural investigations of the heterogeneous deformation indicate that the dominant mechanisms are progressive microcellular collapse followed by foam densification. The phenomenon is compared to the development of a stable neck commonly observed in polymers subjected to uniaxial tension, and a model that describes the densification process is formulated from simple energy balance considerations.     

Potassium geopolymer foams made with silica fume pore forming agent for thermal insulation

Porous potassium based geopolymers with a mutli-scale porosity were synthesized. Silica fume is introduced as an additive to the geopolymer formulation. The free silicon contained inside this silica fume is oxidized in alkaline solution, releasing molecular hydrogen which generates the porosity. Previous work has shown how the porosity can be controlled with temperature, repeated temperature cycles and the mass introduced. Using this protocol, homogeneous foams were made and then studied with scanning electron microscopy. In particular the foam expansion has been followed with time in relation to the microstructure. The thermal conductivity values of the foams were evaluated using a fluxmeter method. The effective thermal conductivities are comprised between 0.12 and 0.35 W m^?1 K^?1 for apparent densities ranging from 0.40 to 0.85 g cm^?3. The corresponding calculated pore volume fractions are in the range of 65–85%. The interest of this material is that it combines the advantages of low bulk density and insulating properties with the characteristics of a geopolymer skeleton. Literature reports a very good fire and acid/base resistance, a low cost of production and the possibility of recycling industrial waste in the form of silica fume.     

Challenge to fortyfold expansion of biodegradable polyester foams by using carbon dioxide as a blowing agent

This paper presents a new foaming technology using supercritical carbon dioxide as a blowing agent to obtain large volume expansions of biodegradable polyester foams of over fortyfold. The basic approach for the promotion of a large volume expansion ratio with carbon dioxide was to prevent cell coalescence by using a branched material, to dissolve carbon dioxide completely in the melt by promoting convective diffusion under a high processing pressure, to reduce the diffusivity of gas by lowering the melt temperature, and to optimize the processing conditions in the die to maximize volume expansion. The desirable composition of the materials includes dehydrated branched biodegradable polyester (polybutylene succinate), CO₂ (blowing agent), and tale (nucleating agent). A single‐screw extrusion system was used for foam processing. A large volume expansion ratio of up to forty‐fivefold was achieved from the biodegradable polyester foams. The morphologies and volume expansion ratios of biodegradable polyester foams at various processing temperatures and pressures were studied.     

Layered-silicate based polystyrene nanocomposite microcellular foam using supercritical carbon dioxide as blowing agent

Exfoliated layered-silicate in the polystyrene (PS) block copolymer with different molecular weights was employed as a model material to investigate the PS nanocomposite microcellular foams expanded by supercritical carbon dioxide. Using a well-controlled foaming procedure, we investigated the influence of molecular weight of PS, dispersion and loading of layered-silicate and pressure drop rate of a blowing agent on the cell size and cell density. Our experimental results indicate that only exfoliated layered-silicate can inhibit the cell expansion and has high nucleation efficiency during foaming. The average cell diameter can be reduced from 6 μm to 1.4 μm and the cell density can be increased from 7.6 × 10⁹ cells/cm³ to 5.0 × 10¹¹ cells/cm³. On the contrary, aggregated layered-silicate in PS did not show any effect on the cell morphology of PS foam.     

Fabrication of in-situ self-reinforced Si3N4 ceramic foams for high-temperature thermal insulation by protein foaming method

To meet demand for lightweight and high-strength ceramic foams, in-situ self-reinforced Si₃N₄ ceramic foams, with compressive strength of 13.2–45.9 MPa, were fabricated by protein foaming method combined with sintered reaction-bonded method. For comparison, ordinary protein foamed ceramics with irregular block microstructure were fabricated via reaction-bonded method, which had compressive strength of 3.6–20.5 MPa. Physical properties of these two types of samples were systematically compared. When open porosity was about 80%, both types of Si₃N₄ ceramic foams had excellent thermal insulation properties (<0.15 W m^?1 K^?1), while compressive strength of in-situ self-reinforced samples increased by more than 158% compared with ordinary samples. Under high-temperature oxidation conditions, microstructures of both types of samples were deformed with increase in oxidation temperature. Moreover, after oxidation temperature was increased to 1400 °C, oxidation weight gain decreased from 18.07% for ordinary samples to only 2.18% for self-reinforced samples. Thus, high-temperature oxidation resistance of Si₃N₄ ceramic foams was greatly improved.     

酚醛泡沫在现代建筑保温工程中的应用及改性研究进展

综述了作为保温材料的酚醛泡沫在国内外的发展及应用情况。酚醛泡沫具有良好的阻燃性能,被发达国家作为优先选用的保温材料,同时在国内知名建筑上得到了很好的应用。采用纳米蒙脱土、聚氨酯预聚体、液体丁腈橡胶、硼酸等改性酚醛泡沫,能不同程度地改变酚醛泡沫的孔结构、力学性能,从而达到提高其韧性的作用。因此,酚醛泡沫在外墙保温市场将具有良好的发展前景。     

Effects of the die geometry on the expansion of polystyrene foams blown with carbon dioxide

This article presents the effects of the die geometry on the expansion ratio of extruded polystyrene foams blown with CO₂. Three groups of interchangeable filamentary dies were used to represent the die parameters. The experimental results reveal that a strong relationship exists between the expansion ratio of the extruded polystyrene foams and the die geometry through its effects on the pressure‐drop rate, the die pressure, the amount of premature cell growth, and the initial shape of the extrudate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A parametric study into the morphology of polystyrene-co-methyl methacrylate foams using supercritical carbon dioxide as a blowing agent

In this study the foaming of poly(styrene-co-methyl methacrylate) (SMMA) using supercritical carbon dioxide is investigated. The effect of different foaming parameters such as temperature and pressure is studied in a quantitative and systematic way, with the aim to control and predict the resulting foam morphology. It is shown that once the polymer properties, such as the glass transition temperature and the solubility of CO₂ are known, full control of the desired foam morphology can be obtained by a proper selection of temperature, pressure and depressurization rate.     

Expansion of polystyrene using water as the blowing agent

Heating of polystyrene beads containing pentane isomers as the blowing agent traditionally produces polystyrene foam. Undesirable emissions of the blowing agent and its high flammability are the complications of this process. A new process for the production of expandable polystyrene has been developed, using water as the blowing agent. Water is trapped inside the polystyrene matrix through the use of starch that is introduced as a separate phase during the suspension polymerization. The problems created by the incompatibility of starch with the organic phase can be partially overcome by “compatibilization” with maleic anhydride. The type of starch can influence the foam morphology of the pre‐expanded beads, while the density is changed only in the range of the experimental error. The density of the pre‐expanded beads is influenced by the blowing technique used (hot air or high frequency electric field). The use of these different blowing techniques does not influence significantly the foam morphology.     

New challenges in polymer foaming: A review of extrusion processes assisted by supercritical carbon dioxide

It is well known that supercritical carbon dioxide (sc-CO₂) is soluble in molten polymers and acts as a plasticizer. The dissolution of sc-CO₂ leads to a decrease in the viscosity of the liquid polymer, the melting point and the glass transition temperature. These properties have been used in several particle generation processes such as PGSS (particles from gas saturated solutions).It is therefore highly likely that extrusion processes would benefit from the use of sc-CO₂ since the rationale of the extrusion processes is to formulate, texture and shape molten polymers by forcing them through a die. Combining these two technologies, extrusion and supercritical fluids, could open up new applications in extrusion.The main advantage of introducing sc-CO₂ in the barrel of an extruder is its function as a plasticizer, which allows the processing of molecules which would otherwise be too fragile to withstand the mechanical stresses and the operating temperatures of a standard extrusion process. In addition, the dissolved CO₂ acts as a foaming agent during expansion through the die. It is therefore possible to control pore generation and growth by controlling the operating conditions.This review focuses on experimental work carried out using continuous extrusion. A continuous process is more economically favourable than batch foaming processes because it is easier to control, has a higher throughput and is very versatile in the properties and shapes of the products obtained.The coupling of extrusion and supercritical CO₂ technologies has already broadened the range of application of extrusion processes. The first applications were developed for the agro-food industry 20 years ago. However, most thermoplastics could potentially be submitted to sc-CO₂-assisted extrusion, opening new challenging opportunities, particularly in the field of pharmaceutical applications.This coupled technology is however still very new and further developments of both experimental and modelling studies will be necessary to gain better theoretical understanding and technical expertise prior to industrial use, especially in the pharmaceutical field.     

Preparation of carbon foams with enhanced oxidation resistance by foaming molten sucrose using a boric acid blowing agent

Boric acid was used as a blowing agent as well as a boron precursor for the preparation of boron-doped carbon foams from molten sucrose. The H⁺ generated, due to the formation of a complex between sucrose and boric acid, catalyzes the –OH to –OH condensation reaction leading to the polymerization and the foaming of the molten sucrose. The char yield of the solid organic foams increased from 24 to 39 wt.% when the boric acid concentration increased from 0 to 8 wt.%, due to the formation of the B–O–C cross-links between sucrose polymer by B–OH to C–OH condensation. The inductively coupled plasma analysis showed the presence of 0.44–3.4 wt.% boron in the carbon foams. The density and compressive strength decreased and cell size increased with boric acid concentration. The room temperature thermal conductivity of the boron-doped carbon foams was in the range of 0.057–0.043 W m⁻¹ K⁻¹. The weight loss studies by dynamic and isothermal heating showed the increased oxidation resistance with boron concentration.