Plasticization of nano‐CaCO3 in polystyrene/nano‐CaCO3 composites

The shear rheological properties of polystyrene (PS)/nano‐CaCO₃ composites were studied to determine the plasticization of nano‐CaCO₃ to PS. The composites were prepared by melt extrusion. A poly(styrene–butadiene–styrene) triblock copolymer (SBS), a poly(styrene–isoprene–styrene) triblock copolymer (SIS), SBS‐grafted maleic anhydride (SBS–MAH), and SIS‐grafted maleic anhydride were used as modifiers or compatibilizers. Because of the weak interaction between CaCO₃ and the PS matrix, the composites with 1 and 3 phr CaCO₃ loadings exhibited apparently higher melt shear rates under the same shear stress with respect to the matrix polymer. The storage moduli for the composites increased with low CaCO₃ concentrations. The results showed that CaCO₃ had some effects on the compatibility of PS/SBS (or SBS–MAH)/CaCO₃ composites, in which SBS could effectively retard the movement of PS chain segments. The improvement of compatibility, due to the chemical interaction between CaCO₃ and the grafted maleic anhydride, had obvious effects on the rheological behavior of the composites, the melt shear rate of the composites decreased greatly, and the results showed that nano‐CaCO₃ could plasticize the PS matrix to some extent. Rheological methods provided an indirect but useful characterization of the composite structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Solid‐state foaming of carbon fiber/polypropylene/nano‐CACO3 composite using supercritical CO2

In this work, nano‐CaCO₃ was used to improve the foamability of carbon fiber (CF)/polypropylene (PP) composite in solid‐state foaming using supercritical CO₂. The CF content was maintained at 15 wt% and four concentrations of nano‐CaCO₃ content, 1, 3, 5 and 8phr, were used. The surface of nano‐CaCO₃ was firstly treated by silane coupling agent. By the way, the properties of the nano‐composites with various nano‐CaCO₃ contents were analyzed by scanning electron microscope (SEM), differential scanning calorimeter (DSC), and torque rheometer. Before foaming, the gas absorption experiment was done using gravimetric method. Concerning on determination of the foaming conditions, it is found that 175°C and 60s were suitable as foaming temperature and time. Furthermore, we can also find that the foamed composites with 3phr nano‐CaCO₃ showed the smallest mean cell diameter and largest cell density compared with the other nano‐CaCO₃ contents under the given saturation condition. In addition, the mean cell diameter decreased while cell density increased as saturation pressure increased because of the higher gas solubility in the composites. When the saturation pressure was 25MPa, the mean cell diameter and cell density with 3phr nano‐CaCO₃ were 17μm and 2.20×10⁷cells/cm³, respectively. POLYM. COMPOS., 35:1723–1735, 2014. © 2013 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.     

Effect of supercritical carbon dioxide on polystyrene extrusion

A study on the extrusion of polystyrene was carried out using supercritical carbon dioxide (scCO₂) as 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 at the passage through the die. For experiments, a single-screw extruder was modified to be able to inject scCO₂ within the extruded material. The effect of operating parameters on material porosity was studied. Samples were characterized by using water-pycnometry, mercury-porosimetry and scanning electron microscopy. Polystyrene with expansion rate about 15–25% was manufactured. A rapid cooling just downstream the die is important to solidify the structure. The die temperature allows the control of the porosity structure. CO₂ concentration shows no significant influence.     

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     

Fabrication of polyamide 12T micro-cellular foams with ultra-high compressive strength via in situ polytetrafluoroethylene fibrillation using supercritical carbon dioxide foaming

The development of micro-cellular foams with ultra-high compressive strength and high volume expansion ratio (VER) is a challenging task. Herein, polyamide 12T (PA12T) micro-cellular foams with ultra-high compressive strength were fabricated via in situ polytetrafluoroethylene (PTFE) fibrillation using supercritical CO₂ foaming technology and a chain extender. The resulting branched structure showed considerably improved viscoelasticity and foaming performance, thus improving the cell morphology of the PA12T foam and exhibiting high VER. The PTFE fibrillation network induced melt strength enhancement, crystallization nucleation, and cell nucleation. The branched PA12T foam with 1.5 wt% PTFE exhibited the smallest cell diameter (15 μm) and highest cell density (3 × 10⁹ cells/cm³). The compressive strength of the foam (0.50 MPa under 5% strain) was 70% higher than that of pure PA12T. This research offers an effective method for producing high-VER PA12T foams with adjustable micro-cellular structures and excellent mechanical properties.     

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     

Properties of calcium carbonate filled and unfilled polystyrene foams prepared using supercritical carbon dioxide

Foaming behaviors of four polystyrenes (PSs) filled and unfilled with various amounts of CaCO₃ using supercritical carbon dioxide were investigated. The PSs include three general purpose grades with different molecular weights (different melt index) and one high impact grade. By adjusting foaming conditions, foam density was determined for each investigated sample. In general, the sample with a lower molecular weight (i.e. higher melt index) yielded a lower foam density for the three general purpose PSs. With the addition of CaCO₃ filler, foam density would increase. The inclusion of rubber in high impact PS was found to complicate its foaming behavior. A qualitative correlation between various types of filled/unfilled PSs and foam density was found in a certain range. An optimum foaming temperature range was required to obtain low foam density for each sample. The corresponding change in matrix modulus by employing various PSs and various filler contents apparently affected the resulting foam density. Although several factors were involved in foaming conditions, the addition of CaCO₃ filler played a significant role in reducing cell size and increasing cell density of the PSs foams investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2276–2284, 2006     

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.     

Polystyrene/CaCO3 composites with different CaCO3 radius and different nano‐CaCO3 content—structure and properties

The Archimedes' principle and physical theory are attempted to analysis the densification and structure of the polystyrene (PS) composites by melt compounding with CaCO₃ having different particle size. The difference between the measured specific volume (ν) andthe theoretically calculated specific volume (ν_mix), Δν = ν−ν_mix, can reflect the densification of the composites. It is clearly demonstrated that the PS composites become more condensed with the reduction of the CaCO₃ particle size. Especially, when the content for nano‐CaCO₃ achieves 2 wt%, the Δν value of the composites reaches the least, which shows the best densification. Meanwhile, the glass transition temperature (T_g) reaches the maximum value of about 100°C by differential scanning calorimetry (DSC) and thermal mechanical analysis (TMA), which indirectly reveals the composites microstructure more condensed. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveal that 2 wt% nano‐CaCO₃ uniformly disperses in PS composites. The CaCO₃ selected in this experiment has certain toughening effect on PS. The impact and tensile strength increase with addition of nano‐CaCO₃, but the elongation at break decreases. When nano‐CaCO₃ content achieved 2 wt%, the impact and tensile strength present the maximum value of 1.63 KJ/m² and 44.5 MPa, which is higher than the pure PS and the composites filled with the same content of micro‐CaCO₃. POLYM. COMPOS., 31:1258–1264, 2010. © 2009 Society of Plastics Engineers     

Preparation, characterization, and supercritical carbon dioxide foaming of polystyrene/graphene oxide composites

Graphene oxide (GO) was prepared by oxidation of graphite using the Hummers method, and was modified by isocyanate to obtain dispersed GO sheets in dimethylformamide. Polystyrene (PS)/GO composites were prepared by solution blending, and their morphologies and properties were characterized. The addition of GO increased the glass transition temperature of the PS/GO composites. The storage modulus and thermal stability of the composites were also improved compared with PS. Foams of PS and PS/GO composites were prepared by supercritical carbon dioxide foaming. The composite foams exhibited slightly higher cell density and smaller cell size compared with the PS foam, indicating the GO sheets can act as heterogeneous nucleation agents.     

PP/超临界CO2连续挤出发泡成型

以超临界CO2为发泡剂,在连续挤出发泡过程中研究了超临界CO2用量对高熔体强度均聚聚丙烯(PP)发泡成型过程的影响.随着超临界CO2用量的增加,发泡挤出机口模压力降低,试样发泡倍率降低,泡孔尺寸变小,泡孔密度提高.在w(CO2)为3%,5%时,得到发泡倍率最高为13左右的PP发泡材料.w(CO2)为7%,发泡温度为12...     

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     

Characterization of expanded polystyrene and its composites by supercritical carbon dioxide foaming approach

Journal of Porous Materials - Supercritical carbon dioxide (scCO2) has been used as a physical blowing agent to produce polymer expanded materials. Firstly, a statistic study was performed to...     

Cell evolution and compressive properties of styrene–butadiene–styrene toughened and calcium carbonate reinforced polystyrene extrusion foams with supercritical carbon dioxide

Polystyrene (PS) foams have been used in various fields, whereas its broader application is limited by its low mechanical strength and brittle features. In this study, styrene–butadiene–styrene (SBS) and calcium carbonate (CaCO₃) nanoparticles were melt‐blended with PS and extrusion‐foamed with supercritical carbon dioxide as a blowing agent to simultaneously toughen and reinforce PS foams. Under the same foaming conditions, the addition of SBS and CaCO₃ was shown to have a significant influence on the cell structure and the compressive properties of the composite foams. We found that the cell structure evolution was highly correlated with the system viscosity. When the rubbery‐phase SBS content was 20%, the cell diameter decreased by 20.7%, and the compressive modulus was enhanced by 289.5%. With the further addition of 5% rigid CaCO₃ nanoparticles, the cell diameter was further reduced by 72.2% and the compressive modulus was improved by 379.2%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43508.     

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.     

Iodine doping of poly(3‐undecylbithiophene) and its composites with polystyrene using supercritical carbon dioxide

Partially doped conductive poly(3‐undecylbithiophene) and its composites with porous, crosslinked polystyrene were chemically doped with iodine using supercritical carbon dioxide to transport iodine to the conductive regions of the composite. The amount of iodine incorporated into the composite increased from 9.3 wt % at ambient conditions without carbon dioxide to 21.4 wt % in the presence of supercritical carbon dioxide. The conductivity of the composite increased by up to two orders of magnitude with iodine doping using supercritical carbon dioxide. The highest conductivity was obtained in samples treated at moderate temperatures and pressures (313 K and 20.7 MPa). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3876–3881, 2003     

Microcellular foaming of silicone rubber with supercritical carbon dioxide

In spite of great concern on the industrial application of microcellular silicone rubber foams, such as in electric and medical devices, only a few works can be found about the foaming of silicone rubber. In this study, microcellular silicone rubber foams with a cell size of 12 μm were successfully prepared with curing by heat and foaming by supercritical CO₂ as a green blowing agent. The microcellular silicone rubber foams exhibited a well-defined cell structure and a uniform cell size distribution. The crosslinking and foaming of silicone rubber was carried out separately. After foaming, the silicone rubber foam was cross-linked again to stabilize the foam structure and further improve its mechanical properties. Foaming process of cross-linked silicone rubber should be designed carefully based on the viscoelastic properties because of its elastic volume recovery in the atmosphere. The basic crosslinking condition for small cell size and high cell density was obtained after investigating the rheological behavior during crosslinking.     

Selective particle distribution and mechanical properties of nano‐CaCO3/ethylene‐propylene‐diene terpolymer/polypropylene composites with high content of nano‐CaCO3

T ernary composite of nano‐CaCO₃/ethylene‐propylene‐diene terpolymer (EPDM)/polypropylene (PP) with high content of nano‐CaCO₃ was prepared by two step compounding route, in which EPDM and nano‐CaCO₃ were mixed first, and then melt compounding with PP matrix. The influence of mixing time during the second compounding on distribution of nano‐CaCO₃ particles and the impact strength of the ternary composite have been investigated. It was found that the Izod impact strength of composite decreased with increasing mixing time. The observation of transmission electron microscopy obviously showed that nano‐CaCO₃ particles transported from EPDM to PP matrix firstly and then from PP to the vicinity of EPDM dispersed phase with the increase of mixing time. This phenomenon can be well explained by the minimization of the dissipative energy and the Young's equation. The scanning electron microscope images show that lots of nano fibrils exist at the interface between nano‐CaCO₃ agglomerates and matrix, which can dissipate lots of energy. The toughening mechanism has been interpreted in terms of three‐stage‐mechanism: stress concentration, void and shear band formation, and induced shear yielding. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nanoplatelet reinforcement of cavity cell walls in polymer foams using carbon dioxide supercritical fluid

Reinforcing the cavity cell walls of polymer foams using nanoparticles can offer a new era for the property‐structure‐processing field in the development of functionalized ultra‐light components and devices manufactured from foam. When the nanoparticles are exfoliated in polymers, the viscosity substantially increases and thus mixing or foaming usually becomes almost impossible. We use CO₂ supercritical fluid (CO₂ SCF) for the mixing and foaming of poly(ethylene‐vinyl acetate) copolymer (EVA) with montmorillonite (MMT) nanoplatelets. The in situ evaporation of CO₂ induces robust cavity cells of the EVA/MMT nanocomposite foam in a stable form of spherical shapes, which are seldom achieved by other methods. As the bubble grows and becomes stabilized in CO₂ SCF, the exfoliated MMT nanoparticles are aligned at the cell walls by the Gibbs adsorption principle to minimize the surface energy at the gas–liquid interface and increase the rupture strength of the cavity walls. It is demonstrated that the developed methodology can be successfully used for foaming EVA containing high vinyl acetate (VA) content (>40%). Since EVA is too soft to construct cell walls of foam using conventional methods, the applicability of the developed methodology is extensively broadened for superior adhesion and compatibility with other materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46615.