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.     

Effect of supercritical carbon dioxide on morphology development during polymer blending

Supercritical carbon dioxide (scCO₂) was added during compounding of polystyrene and poly(methyl methacrylate) (PMMA) and the resulting morphology development was observed. The compounding took place in a twin screw extruder and a high‐pressure batch mixer. Viscosity reduction of PMMA and polystyrene were measured using a slit die rheometer attached to the twin screw extruder. Carbon dioxide was added at 0.5, 1.0, 2.0 and 3.0 wt% based on polymer melt flow rates. A viscosity reduction of up to 80% was seen with PMMA and up to 70% with polystyrene. A sharp decrease in the size of the minor (dispersed) phase was observed near the injection point of CO₂ in the twin screw extruder for blends with a viscosity ratio, ηPMMA/ηpolystyrene, of 7.3, at a shear rate of 100 s^?1. However, further compounding led to coalescence of the dispersed phase. Adding scCO₂ did not change the path of morphology development; however, the final domain size was smaller. In both batch and continuous blending, de‐mixing occurred upon CO₂ venting. The reduction in size of the PMMA phase was lost after CO₂ venting. The resulting morphology was similar to that without the addition of CO₂. Adding small amounts of fillers (e.g. carbon black, calcium carbonate, or nano‐clay particles) tended to prevent the de‐mixing of the polymer blend system when the CO₂ was released. For blends with a viscosity ratio of 1.3, at a shear rate of 100 s^?1, the addition of scCO₂ only slightly reduced the domain size of the minor phase.     

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.     

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.     

Supercritical carbon dioxide assisted blending of polystyrene and poly(methyl methyacrylate)

A method for blending polystyrene and poly(methyl methacrylate), (PMMA), with the addition of supercritical carbon dioxide has been investigated. The first series of blends was a PMMA and polystyrene with similar melt viscosities. The second series of blends was a PMMA and polystyrene with a viscosity ratio (ηPMMA/ηpolystyrene) of about 20. The results show that a reduction in the size of the minor or dispersed phase is achieved when supercritical carbon dioxide is added to the blend system. A high-pressure mixing vessel was used to prepare the blends under pressure with carbon dioxide for batch blending. The solubilities of CO₂ in PMMA and polystyrene, measured in the high-pressure mixing vessel at 200°C and 13.78 MPa (2000 psi) was 5.8 and 3.6 wt%, respectively. A single screw extruder was used to study the effects of carbon dioxide on the viscosity of polymer melts. The melt viscosity of PMMA was reduced by up to 70% with approximately 0.4 wt% CO₂. The melt viscosity of polystyrene was reduced by up to 56% with a CO₂ content of 0.3 wt%. A twin screw extruder was used to study the effects of injecting carbon dioxide in a continuous compounding operation.     

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.     

共混比对丁腈橡胶/氯醚橡胶性能的影响

研究了共混比时常规共混及动态硫化共混丁腈橡胶(NBR)／氯醚橡胶(ECO)的力学性能及加工流变性能的影响。结果表明,共混比对NBR／ECO胶料的力学性能及加工流变性能影响显著。NBR经动态硫化后,压缩永久变形及挤出胀大明显减小,拉伸强度提高,表现黏度随ECO用量的增大而减小。共混比对常规共混胶的表观黏度影响不大。动态硫化有利于改善NBR／ECO胶料的加工性能。     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

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...     

Preparation of titanium dioxide/activated carbon composites using supercritical carbon dioxide

The penetration of titanium tetraisopropoxide (TTIP) dissolved in supercritical CO₂ into the nano-spaces of an activated carbon was studied for the preparation of a TiO₂-coated activated carbon. The conversion of TTIP to TiO₂ through thermal decomposition was confirmed by evolved gas analysis during heat treatment under a N₂ flow. Acetone was detected in the evolved gas, which suggested that some isopropoxide groups in TTIP reacted with the carbonyl groups on the activated carbon surface. This chemical reaction with carbon is expected to be advantageous for favorable attachment to the carbon surface. The crystallite size of anatase in the TiO₂/carbon composites was 4.1 nm, as estimated from the X-ray diffraction pattern, which almost corresponded to the graphene crystallite size; L_a (3.3-3.4 nm), as estimated from both the Raman spectrum and X-ray diffraction pattern. As the size of the crystallite prepared by bulk condensation of TTIP was more than 15 nm, these results confirmed that the anatase crystals were present in the carbon pores. Also, it was suggested that the crystal growth of TiO₂ was influenced by the carbon nano-spaces.     

Foam processing of poly(ethylene-co-vinyl acetate) rubber using supercritical carbon dioxide

Soft rubber foams like poly(ethylene-co-vinyl acetate) (EVA) are industrially applied in a broad range of products, including sports gear, insulation materials and drug delivery systems. In contrast to glassy polymers, few studies in literature concern the foaming of soft rubbers using supercritical carbon dioxide. In this study, open microporous matrices of EVA have been formed with CO₂. Prior to the foam expansion, sorption and swelling isotherms of CO₂ in EVA have been measured and the obtained isotherms have been correlated using the Sanchez-Lacombe equation of state. Additionally, a pressure-independent diffusion coefficient of CO₂ in EVA has been obtained from these experiments. The microporous foams have been formed by a pressure quench of the CO₂-swollen polymer matrix. Sorption pressure as well as temperature and decompression times appear to determine the pore size and bulk density of the foam. These parameters allow for a control of the foam structure of EVA rubbers.     

橡胶共混和橡塑共混

该文从高分子材料的共混理论着手探讨了橡胶共混材料的选择,共混体系的设计,以及共混加工条件的确定。此文还讨论了共混物的结构形态及其转换。文章涉及了共混的新热点一动态硫化,并举了实例。     

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.     

反应共混改性纳米二氧化硅/炭黑填充溶聚丁苯橡胶的结构与性能

采用动态反应共混法制备了含硫的硅烷偶联剂双-[γ-(三乙氧基硅)丙基]-四硫化物(Si-69)和双-[γ-(三乙氧基硅)丙基]-二硫化物(Si-75)改性纳米SiO2/炭黑填充溶聚丁苯橡胶(SSBR)硫化胶,分析了胶料的微观结构,研究了胶料的物理机械性能和动态力学性能等。结果表明,纳米填料在胶料中呈现较理想的分散状态;当纳米SiO2与炭黑填料的总量为70份时,随改性纳米SiO2用量的增加,SSBR硫化胶的邵尔A硬度、扯断伸长率、永久变形、撕裂强度下降,拉伸强度变化不大,300%定伸应力显著提高,生热明显下降,其中Si-75改性纳米SiO2/炭黑填充的SSBR综合性能更优;纳米填料在橡胶基体中的分散性好,胶料的动态生热低。     

超临界二氧化碳中再生硫化天然橡胶的影响因素及脱硫效果

以二苯基二硫化物(DD)为脱硫剂,在超临界CO2作用下对硫化天然橡胶(NR)进行了脱硫再生,考察了CO2密度、反应温度和压力以及反应时间等对脱硫作用的影响,并对脱硫降解产物进行了相对分子质量测定和核磁共振表征。结果表明,采用超临界CO2流体为溶剂可以实现对硫化NR的脱硫降解,脱硫降解条件为CO2的密度不小于0.4722g/cm3、反应温度不低于160℃、反应时间不少于90min;溶胶率随降解温度的提高和时间的延长而增大;在降解过程中除了S—S、S—C断裂外还发生了部分主链断裂,降解后橡胶相对分子质量下降;脱硫剂DD能有效打开硫交联键,脱硫降解后再生胶分子中引入了少量的苯环结构。     

Cell structure and impact properties of foamed polystyrene in constrained conditions using supercritical carbon dioxide

To obtain cellular with small cell diameter, to control cell structure and to improve impact strength of foaming materials, the quick-heating method was applied for foaming polystyrene (PS) using supercritical CO₂ (Sc-CO₂) as physical blowing agent. Then, changes of cell structure and impact strength in microcellular foamed PS materials under constrained conditions were studied. The effects of foaming processing parameters, such as foaming temperature, saturation pressure and foaming time on the cell structure and impact strength of foamed PS in the constrained conditions were studied. The results showed that the Sc-CO₂ solubility and nucleation density in the constrained conditions were not influenced compared with those under free foaming conditions. However, cells in constrained foaming process are mostly circular and independent with thick cell walls; the phenomenon of cell coalescence and collapse was effectively eliminated under constrained conditions. In addition, cell diameters in constrained foaming process decrease with increase in foaming temperature and increase with increase in the foaming time. Compared with that in free foaming conditions, the cell growth was restrained dramatically under constrained conditions which resulted in smaller cell diameter. Moreover, higher impact strength could be obtained for foamed PS as foaming time was prolonged, foaming temperature was increased or saturation pressure was enhanced.     

A comparative study of poly(methyl methacrylate) and polystyrene/clay nanocomposites prepared in supercritical carbon dioxide

Poly(methyl methacrylate) and polystyrene/clay nanocomposites have been prepared via pseudo-dispersion polymerizations in the presence of a poly(dimethylsiloxane) surfactant-modified clay (PDMS-clay) in supercritical carbon dioxide. The effects of the PDMS-clay concentration on polymer conversion, molecular weight, and morphology have been investigated. The insoluble dispersion of PDMS-clay is shown to be an effective stabilizer for both MMA and styrene polymerization in scCO₂. The nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). While XRD shows featureless patterns for both nanocomposites, the actual distributions of clay are found to be quite different between PMMA and PS nanocomposites, presumably due to the different interaction mechanisms between the polymers and clay. Consequently, the different states of clay in the two nanocomposites play an important role in the mechanical properties of the nanocomposites, and a to a lesser degree in the thermal properties.     

Sorption of C. I. Disperse Red 60 in polystyrene and PMMA films and polyester and Nylon 6 textiles in the presence of supercritical carbon dioxide

C. I. Disperse Red 60 (DR60) was absorbed into polymer films and textile fibers in the presence of supercritical carbon dioxide at pressures between 5 and 33MPa and at temperatures between 308.2 and 423.2 K. Polystyrene (PS) and poly(methyl methacrylate) (PMMA) films and polyester (polyethylene terephthalate: PET) and Nylon 6 textiles were used as absorbents. The amount of equilibrium sorption of dye increased both with pressure and temperature. The sorption behavior was successfully analyzed with the quasi dual-mode sorption model.     

Studies on phase equilibria of a multicomponent model mixture in supercritical carbon dioxide and trifluoromethane

Phase equilibria were studied of a multicomponent model mixture representing the middle distillate of a coal liquefaction product in the gases carbon dioxide and trifluoromethane at temperatures (308–338 K) and pressures (6–30 MPa) above the critical points of the gases. Partition coefficients and separation factors were determined for the individual mixture components by analysing samples from the coexisting phases. The results show that selectivity due to structural properties (π-bonds, dipole moments, etc.) is superimposed by selectivity due to differences in vapor pressures. The concepts of structure selectivity and vapor pressure selectivity are introduced and changes of these parameters with pressure and temperature are reported. Enhancement factors in the carbon dioxide/model mixture system were calculated and show good agreement with the experimental results.     

Synthesis of biodiesel in supercritical alcohols and supercritical carbon dioxide

Biodiesel was synthesized in supercritical fluids by two routes: non-catalytically in supercritical alcohols and by enzyme catalysis in supercritical carbon dioxide. Two oils, sesame oil and mustard oil, and two alcohols, methanol and ethanol, were used for the synthesis. Complete conversion was observed for synthesis in supercritical alcohols whereas only a maximum of 70% conversion was observed for the enzymatic synthesis in supercritical carbon dioxide. For the synthesis in supercritical alcohols, the activation energies and pseudo-first order rate constants were determined. For the reactions in supercritical carbon dioxide, a mechanism based on ping pong bi-bi was proposed and the kinetic parameters were determined.