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.     

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     

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.     

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     

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     

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.     

Processing and compressive strengths of syntactic foams with and without fibrous reinforcements

Syntactic foam composites containing 0, 0.9, 1.76, 2.54, 3.54, and 4.5 vol % of E‐glass fibers in the form of chopped strands were fabricated and subjected to compression testing. It was found that the compressive strength values generally increased with fiber content except for the 3.54% fiber‐bearing cast slab, which recorded lower values. This lone exception was due to the difference in processing route adopted in fabricating this particular fiber‐bearing foam. Also noticed was the fact that the compressive strength of the 0.9 vol % fiber‐bearing system was lower compared to the fiber‐free system. This was correlated to the higher level of void content noticed with this fiber‐bearing foam compared to that seen in the unreinforced foam. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 405–411, 2001     

Synthesis of montmorillonite/polystyrene nanocomposites in supercritical carbon dioxide

Monomer styrene and initiator N,N′‐azobis(isobutyronitrile) were impregnated into montmorillonite (MMT) galleries using supercritical CO₂ at 35°C and 12.0 MPa, after thermal polymerization of monomer at 65°C, resulting in MMT/polystyrene nanocomposites. The morphology and structure of the products were characterized by FTIR, powder X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results indicate that MMT is dispersed in the composite with intercalated and exfoliated structures, enhancing the thermal stability of nanocomposites. Changing the soaking time and the content of MMT in the supercritical solution during the impregnating process can control the exfoliated extent of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1194–1197, 2004     

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     

Toward an understanding of how red phosphorus and expandable graphite enhance the fire resistance of expandable polystyrene foams

Flame retardant expandable polystyrene (EPS) foams were prepared by coating method. Red phosphorus (RP) and expandable graphite (EG) were chosen as the flame retardants to be coated on the surface of expanded PS beads. By the presence of 33 phr RP/EG with a mass ratio of 1:1, the limiting oxygen index of EPS foam could reach up to 26.9%, with V-0 rating obtained in UL-94 test. The peak heat release rate could also decrease to 180.67 kW/m², which was 72.9% lower than that of neat EPS sample. Thermogravimetric analysis revealed an obvious increase of thermal stability and residue char amount by the presence of RP and EG. From the observation and analysis of char residue, it could be proposed that there existed a significant synergistic effect between RP and EG. RP could be oxidized and further react with graphite by the presence of oxygen at high temperature, forming isolated char layer and releasing nonflammable gases. Moreover, P radicals were generated at high temperature and could capture the radicals formed during the combustion of polystyrene and eliminate the burning chain reactions.     

The influence of in situ synthesized nanoparticles on microstructure and compression properties of polymer foams during supercritical carbon dioxide foaming

The influence of in situ synthesized nanoparticles on the microstructure and compression properties of polymer foams during supercritical carbon dioxide foaming has been investigated. The in situ synthesized Ag nanoparticles were chosen to be heterogeneous nucleating agent. For achieving our target, the influence of the nanoparticle size on the cell structure and the nucleation mechanism has been detailed discussed firstly. The results show that the in situ synthesized nanoparticles can be heterogeneous nucleation agent to improve the cell density of the PMMA‐based foams. The particle size is able to reduce to the critical size of heterogeneous nucleation agent and, then, can highly improve the cell density of the foams. The Ag nanoparticles with average size of 2.2 nm led to 85% increase in compressive strength of the foams. The improvement of strength of the polymer matrix and the microstructure of the foams can lead to the remarkable increase in the mechanical properties of the foams. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44629.     

Effects of polyphenylene oxide content on morphology,thermal, and mechanical properties of polyphenylene oxide/polyamide 6 blends

A series of composites of PPO/PA 6 with improved toughness were synthesized by using ε‐caprolactam as a reactive solvent. Inserting minor PPO macromolecules (1–3 wt %) into PA 6 matrix obviously reduced the crystallinity of PA6. Two crystallization temperatures were found when 6 wt % PPO was added. SEM revealed that the phase morphology of the composites could be manipulated by varying the content of PPO in PA 6. As a consequence, the impact strength and the elongation of PPO/PA6 were improved with maintenance of tensile strength when quite small content of PPO (1–3 wt %) was incorporated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Improving the fire performance and smoke suppression of expandable polystyrene foams by coating with multi-dimensional carbon nanoparticles

Expandable graphite (EG) and modified multi-wall carbon nanotubes (ATH-MWNT) were introduced to expandable polystyrene (EPS) foams in order to improve its fire performance. The fire performance of EPS foams was evaluated by limiting the oxygen index (LOI), vertical burning (UL-94), and cone calorimetry tests. The results showed that the presence of 14.3% EG and 4.1% ATH-MWNT increased the LOI value from 18.0 to 30.3%, upgraded the UL-94 rating from no rating to V-0, completely eliminated melt dripping, and significantly decreased the peak heat release rate from 933 to 177 kW/m². Thermal analysis indicated that the thermal stability and char formation were improved by the presence of flame retardants. The char morphology was characterized by scanning electronic microscopy (SEM). It was suggested that the presence of EG and ATH-MWNT could form integrated char layers during combustion, which was beneficial to the formation of an intumescent protective char structure.     

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     

Preparation of poly(propylene carbonate)/nano calcium carbonate composites and their supercritical carbon dioxide foaming behavior

Biodegradable polymer foams are attracting extensive attention in both academic and industrial fields. In this study, an emerging biodegradable polymer, poly(propylene carbonate) (PPC), was compounded with nano calcium carbonate (nano‐CaCO₃) and foamed via supercritical carbon dioxide for the first time. Four concentrations of nano‐CaCO₃, 1, 3, 5, and 10 wt %, were used and the thermal properties of PPC/nano‐CaCO₃ composites were investigated. The glass‐transition temperature and thermal decomposition temperature of the PPC/nano‐CaCO₃ composites increased with the addition of nano‐CaCO₃. The morphologies of the PPC/nano‐CaCO₃ composites and the rheological results showed that homogeneous dispersions of nano‐CaCO₃ and percolated nano‐CaCO₃ networks were achieved at a nano‐CaCO₃ content of 3 wt %. Therefore, the finest cell diameter (3.13 μm) and highest cell density (6.02 × 10⁹ cells/cm³) were obtained at the same nano‐CaCO₃ content. The cell structure dependences of PPC and PPC with a nano‐CaCO₃ content of 3 wt % (PPC‐3) foams on the foaming pressure and temperature were investigated as well. The results suggested that the cell structure of PPC‐3 was more stable at different foaming conditions due to the networks of nano‐CaCO₃. Moreover, the change in pressure was more influential on the cell structure than the temperature. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42248.     

Environmental effects on the strength and impact damage resistance of alumina based oxide/oxide ceramic matrix composites

In this study the effects of high temperature and moisture on the impact damage resistance and mechanical strength of Nextel 610/alumina silicate ceramic matrix composites were experimentally evaluated. Composite laminates were exposed to either a 1050°C isothermal furnace-based environment for 30 consecutive days at 6 h a day, or 95% relative humidity environment for 13 consecutive days at 67°C. Low velocity impact, tensile and short beam strength tests were performed on both ambient and environmentally conditioned laminates and damage was characterized using a combination of non-destructive and destructive techniques. High temperature and humidity environmental exposure adversely affected the impact resistance of the composite laminates. For all the environments, planar internal damage area was greater than the back side dent area, which in turn was greater than the impactor side dent area. Evidence of environmental embrittlement through a stiffer tensile response was noted for the high temperature exposed laminates while the short beam strength tests showed greater propensity for interlaminar shear failure in the moisture exposed laminates. Destructive evaluations exposed larger, more pronounced delaminations in the environmentally conditioned laminates in comparison to the ambient ones. External damage metrics of the impactor side dent depth and area directly influenced the post-impact tensile strength of the laminates while no such trend between internal damage area and residual strength could be ascertained.     

High‐temperature oxidation and compressive strength of Cr2AlC MAX phase foams with controlled porosity

Cr₂AlC foams have been processed for the first time containing low (35 vol%), intermediate (53 vol%), and high (75 vol%) content of porosity and three ranges of pore size, 90‐180 μm, 180‐250 μm, and 250‐400 μm. Sacrificial template technique was used as the processing method, utilizing NH₄HCO₃ as a temporary pore former. Cr₂AlC foams exhibited negligible oxidation up to 800°C and excellent response up to 1300°C due to the in‐situ formation of an outer thin continuous protective layer of α‐Al₂O₃. The in‐situ α‐Al₂O₃ protective layer covered seamlessly all the external surface of the pores, even when they present sharp angles and tight corners, reducing significantly the further oxidation of the foams. The compressive strength of the foams was 73 and 13 MPa for 53 vol% and 75 vol% porosity, respectively, which increased up to 128 and 24 MPa after their oxidation at 1200°C for 1 hour. The increase in the compressive strength after the oxidation was caused by the switch from inter‐ to transgranular fracture mode. According to the excellent high‐temperature response, heat exchangers and catalyst supports are the potential application of these foams.     

Synthesis of zinc oxide nanoparticles and their effect on the compressive strength and setting time of self-compacted concrete paste as cementitious composites

In the present study, the mechanical properties of self-compacting concrete were investigated after the addition of different amounts of ZnO nanoparticles. The zinc oxide nanoparticles, with an average particle size of about 30 nm, were synthesized and their properties studied with the help of a scanning electron microscope (SEM) and X-ray diffraction. The prepared nanoparticles were partially added to self-compacting concrete at different concentrations (0.05, 0.1, 0.2, 0.5 and 1.0%), and the mechanical (flexural and split tensile) strength of the specimens measured after 7, 14, 21 and 28 days, respectively. The present results have shown that the ZnO nanoparticles were able to improve the flexural strength of self-compacting concrete. The increased ZnO content of more than 0.2% could increase the flexural strength, and the maximum flexural and split tensile strength was observed after the addition of 0.5% nanoparticles. Finally, ZnO nanoparticles could improve the pore structure of the self-compacted concrete and shift the distributed pores to harmless and less-harmful pores, while increasing mechanical strength.     

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.     

Comparison of nanoclay and carbon nanofiber particles on rheology of molten polystyrene nanocomposites under supercritical carbon dioxide

The effects of nanoparticles and high‐pressure carbon dioxide (CO₂) on shear viscosity of polystyrene (PS) were studied. Master curves of PS, PS + 5 wt % carbon nanofibers (CNFs), and PS + 5 wt % nanoclay (Southern Clay 20A) without CO₂ were created based on parallel‐plate measurements. The results showed that addition of nanoparticles increased the viscosity of the neat polymer. Steady‐state shear viscosity of PS in the presence of CO₂ and nanoparticles was measured by a modified Couette rheometer. The effect of supercritical CO₂ on these systems was characterized by shift factors. It was found that under the same temperature and CO₂ pressure, CO₂ reduced the viscosity less for both PS‐20A and PS‐CNFs than neat PS. Between the two types of nanoparticles, CNFs showed a larger viscosity reduction than 20A, indicating a higher CO₂ affinity for CNFs than 20A. However, the advantage of CNFs over 20A for larger viscosity reduction decreased with higher temperature. A gravimetric method (magnetic suspension balance) was used to measure the excess adsorption of CO₂ onto CNFs and nanoclay, thus, CO₂ showed a higher affinity for CNFs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010