Modification of polystyrene properties by CO2: Experimental study and correlation

The sorption of CO₂ in polymers entails their swelling and plasticization whose study is crucial for the design of processes and further applications. The operating conditions during foaming, purification, or impregnation of polymers in CO₂ are mainly determined by the mentioned binary system. In this work, the modification of polystyrene's physical properties (glass transition temperature and viscosity) has been experimentally studied. Since plasticization phenomena are very valuable for the processing of polymers, the amount of CO₂ absorbed into the polymer is related with the changes in the described properties. Furthermore, interfacial tension is also correlated with the sorption of CO₂ from literature data. The proposed correlation fits pretty well the properties shifts in the studied working conditions. Finally, the influence of pressure and temperature on the diffusivity of the CO₂ in the polystyrene is calculated through the measurement of viscosity along time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41696.     

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     

Crystal morphology and transcrystallization mechanism of isotactic polypropylene induced by fibres: interface nucleation versus bulk nucleation

Using polarized optical microscopy (POM) equipped with a hot stage, morphological investigations of an isotactic polypropylene (iPP) matrix, induced by a homogeneous iPP fibre and heterogeneous pure/modified nylon 6 fibres, were carried out. With respect to transcrystallization related to heterogeneous nucleation on the surface of the fibre, the nucleation mode was found to be different for iPP fibres and nylon 6 fibres. An iPP fibre can serve as a macroscopic linear nucleus, similarly to the shish‐type structure formed in stress‐induced crystallization, to induce kebab‐like growth of lamellae, whereas numerous closely packed spherulites along nylon 6 fibres resulted in macroscopic transverse growth to form a transcrystallite owing to the limitation along the fibre axis. The difference in nature between these two transcrystallites can be further demonstrated by their optical characters related to the lamellar arrangement inside the transcrystallite. As for homogeneous iPP composites, the formation of transcrystallites results from lattice matching, in consideration of the same chemical structure and lattice parameters between fibre and matrix. The incorporation of calcium chloride into a nylon 6 fibre—to destroy its crystal structure—confirmed the role of lattice matching between nylon 6 fibre and iPP matrix. The addition of atactic polypropylene (aPP) in order to enhance the nucleation ability of the iPP matrix also greatly weakened transcrystallization. Our work demonstrates that transcrystallization is just a matter of competition between interface nucleation and bulk nucleation, namely, if interface nucleation is faster than bulk nucleation, transcrystallization will develop. If not, it will be suppressed. Copyright © 2006 Society of Chemical Industry     

CO2 foaming of poly(ethylene glycol)/polystyrene blends: Relationship of the blend morphology,CO2 mass transfer,and cellular structure

When polymer blends are foamed by physical foaming agents, such as CO₂ or N₂, not only the morphology and viscosity of the blend polymers but also the solubility and diffusivity of the physical foaming agents in the polymers determine the cellular structure: closed cell or open cell and monomodal or bimodal. The foam of poly(ethylene glycol) (PEG)/polystyrene (PS) blends shows a unique bimodal (large and small) cellular structure, in which the large‐size cells embrace a PEG particle. Depending on the foaming condition, the average size of the large cells ranges from 40 to 500 μm, whereas that of small cells becomes less than 20 μm, which is smaller than that of neat PS foams. The formation mechanism of the cellular structure has been investigated from the viewpoint of the morphology and viscosity of the blend polymer and the mass‐transfer rate of the physical foaming agent in each polymer phase. The solubility and diffusivity of CO₂, which determine the mass‐transfer rate of CO₂ from the matrix to the bubbles, were measured by a gravimetric measurement, that is, a magnetic suspension balance. The solubility and diffusivity of CO₂ in PS differed from those in PEG: the diffusion coefficient of CO₂ in PEG at 110°C was 3.36 × 10^?9 m²/s, and that in PS was 2.38 × 10^?10 m²/s. Henry's constant in PEG was 5600 cm³ (STP)/(kg MPa) at 110°C, and that in PS was 3100 cm³ (STP)/(kg MPa). These differences in the transport properties, morphology of the blend, and CO₂‐induced viscosity depression are the control factors for creating the unique cellular structure in PEG/PS blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1899–1906, 2005     

Scaling laws and polystyrene networks: a quasi-elastic light scattering study

Randomly crosslinked networks with a range of crosslink densities were prepared by γ-irradiation. Quasielastic light scattering measurements were made on the gels swollen to equilibrium in cyclohexane at 308, 318 and 333 K. The longitudinal osmotic modulus M_os was obtained from the intensity of the dynamically scattered light, and the cooperative diffusion coefficient D_c calculated from the relaxation rate of the autocorrelation function. The concentration dependence of these parameters at the theta temperature was found to be consistent with the scaling predictions, but at higher temperatures where excluded volume conditions prevail, deviations from scaling behaviour were observed. These discrepancies are probably caused by defects in the network structure.     

Effect of the molecular weight between crosslinks of thermally cured epoxy resins on the CO2‐bubble nucleation in a batch physical foaming process

Epoxy resins (bisphenol A type epoxy resins/2‐ethyl‐4‐methylimidazole) consisting of oligomers with different molecular weights were foamed using a temperature‐quench physical foaming method with CO₂. The resulting cell morphologies could be classified into four types: non‐foamed structure, cracked structure, star‐shaped structure, and sphere‐shaped structure. The effects of the gel fraction and molecular weight between crosslinks (M_C) on the cell morphology were investigated for the preparation of microcellular epoxy foams. M_C was calculated by measuring the plateau rubber modulus of the rheological properties and the weight uptake of acetone. By varying the molecular weight of the epoxy oligomers and the cure time, the M_C of the epoxy was controlled to modulate the cell morphology. The experiments elucidated the threshold M_C value that permits CO₂‐bubble nucleation: CO₂‐bubble nucleation in the epoxy resin could be induced when the distance between the crosslinking points exceeded the critical size of bubble nucleus. Based on this information, the microcellular epoxy foam was prepared by maintaining M_C above 10⁴g mol⁻¹ and the complex modulus above 6 × 10⁸ Pa. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40407.     

The micromechanics and microstructure of CO2 crazes in polystyrene

Although CO₂ at 1 atmosphere pressure is not a crazing and/or cracking agent for polystyrene (PS), we have established that it becomes one at higher pressure. Crazes grown from cracks in PS thin films in high pressure CO₂ are investigated using transmission electron microscopy (TEM). The fact that broken craze fibrils retract strongly upon exposure to high pressure CO₂ gas suggests that the primary effect of the CO₂ is plasticization, not surface energy reduction. Quantitative analyses of TEM micrographs of crazes grown at CO₂ pressures in the range 5 to 100 MPa at 34°C and 45°C have been carried out to find the craze fibril volume fractions v_f(x) and the surface displacements w(x) along each craze. From the fibril volume fraction profile along the craze, the dominant craze thickening mechanism of CO₂ crazes is shown to be the same as that for air crazes, i.e. the surface drawing mechanism, and not the fibril creep mechanism. The craze surface stress profile is computed from the craze surface displacements using a distributed dislocation analysis. These profiles all show a stress concentration at the craze tip which falls to a roughly constant value σ_b, over the rest of the craze. The fracture toughness G_Ic (and critical stress intensity factor K_Ic) for propagation of a crack in PS at these CO₂ pressures can also be computed. All these quantities (V_f, σ_b, G_Ic and K_Ic) show pronounced minima as a function of CO₂ pressure at 20 MPa, the same CO₂ pressure at which T_g of the polymer also reaches a minimum. These minima are more pronounced at 45°C than at 34°C. The G_Ic's and K_Ic's are depressed by orders of magnitude at the minimum, which corresponds to the qualitative observation that CO₂ becomes a severe cracking agent at these pressures. These observations provide additional confirmation that the major mechanism for the environmental crazing and cracking of PS by CO₂ is plasticization of the craze fibrils and surfaces.     

Beyond classical theory: Predicting the free energy barrier of bubble nucleation in polymer foaming

Based on the Gibbs‐Tolman‐Koenig formalism, we considered the Tolman correction to the free energy barrier of bubble nucleation in polymer‐gas binary mixtures. For this class of systems, the correction may be estimated with a reasonable accuracy using experimentally accessible macroscopic thermodynamic quantities only. Although the Tolman correction is applicable only in the low supersaturation regime, a simple ansatz regarding the supersaturation dependence of the Tolman length can be made to extend the usefulness of this approach and to yield the free energy barrier that vanishes at the mean‐field spinodal as demanded by thermodynamic considerations. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3042–3053, 2013     

Supercritical CO2 assisted processing of polystyrene/nylon 1212 blends and CO2‐induced epitaxy on nylon 1212

Polystyrene/nylon 1212 blends were prepared with supercritical CO₂ as the substrate swelling agent and monomer/initiator carrier. Original nylon 1212 and blends were characterized with differential scanning calorimetry (DSC), polarizing microscopy, wide‐angle X‐ray diffraction, and scanning electron microscopy (SEM). A novel phenomenon, CO₂‐induced epitaxy, was discovered, and its mechanism was deduced. Thermal analysis performed with DSC indicated that the polystyrene/nylon 1212 blends had thermal stability superior to that of virgin nylon 1212. The DSC and SEM measurements indicated that incorporated polystyrene could notably improve the mechanical performance of nylon 1212. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2023–2029, 2004     

Miscible blends of syndiotactic polystyrene and atactic polystyrene. Part 2. Depolarized light scattering studies and crystal growth rates

Crystallization kinetics and morphology in miscible blends of syndiotactic polystyrene (sPS) and atactic postyrene (aPS) have been investigated by means of time-resolved depolarized light scattering (DPLS), polarized optical microscopy (POM) and scanning electron microscopy (SEM). Two different weight-average molecular weight of aPS, i.e. M_w=100k and 4.3k, were used to prepare the blends and denoted sPS/aPS(H) and sPS/aPS(M), respectively. Owing to a dilution effect, addition of aPS reduces the crystal growth rate and the overall crystallization rate of sPS; the reduction is more significant in sPS/aPS(M) of which a depression of equilibrium melting temperature is found due to the enhanced mixing entropy. Linear crystal growth is always observed in sPS/aPS(H) at the temperatures studied (240-269 °C) and results in an interfibrillar segregation morphology revealed by SEM, whereas sPS/aPS(M) with high aPS content exhibits non-linear growth behavior at low supercooling and gives an interspherulitic segregation morphology. Based on the Lauritzen-Hoffman theory, the fold surface free energies (σ_e) of sPS lamellae derived from DPLS and POM are in fair agreement, being 15.1 erg/cm² from the former and 12.6 erg/cm² from the latter. The peculiarly low values of σ_e and the derived work of chain folding are discussed briefly. On addition of aPS, the lateral surface free energy of lamellae remains intact (9.9 erg/cm²) regardless of aPS molecular weight used, which is ascribed to the absence of specific interaction between sPS and aPS components. Moreover, it seems that the activation energy for sPS chains to diffuse from the miscible melt to the crystal growth front is slightly increased in sPS/aPS(M), plausibly attributable to the extra energy required for the demixing process.     

Effect of surface curvature and wettability on nucleation of methane hydrate

Natural gas hydrate nucleation is a complex physical and chemical process that is not well understood presently. In this article, an improved thermodynamic model is proposed to analyze the effects of surface curvature and wettability on methane hydrate nucleation for the first time. The results indicate that methane hydrate nucleation is more difficult on hydrophilic curvature surfaces under the same conditions, with a larger critical nucleation radius and required energy barrier than on hydrophobic surfaces. Furthermore, a convex surface is more favorable for forming methane hydrate under the same conditions than a concave surface. The model's results are critical in elucidating the microscopic mechanism of methane hydrate nucleation and providing a theoretical foundation for developing technologies for strengthening and inhibiting hydrate formation.     

The synergy of supercritical CO2 and supercritical N2 in foaming of polystyrene for cell nucleation

This study examines the foaming behaviour of polystyrene (PS) blown with supercritical CO₂–N₂ blends. This is achieved by observing their foaming processes in situ using a visualization system within a high-temperature/high-pressure view-cell. Through analyzing the cell nucleation and growth processes, the foaming mechanisms of PS blown with supercritical CO₂–N₂ blends have been studied. It was observed that the 75% CO₂–25% N₂ blend yielded the highest cell densities over a wide processing temperature window, which indicates the high nucleating power of supercritical N₂ and the high foam expanding ability of supercritical CO₂ would produce synergistic effects with that ratio in batch foaming. Also, the presence of supercritical CO₂ increased the solubility of supercritical N₂ in PS, so the concentration of dissolved supercritical N₂ was higher than the prediction by the simple mixing rule. The additional supercritical N₂ further increased the cell nucleation performance. These results provide valuable directions to identify the optimal supercritical CO₂–N₂ composition for the foaming of PS to replace the hazardous blowing agents which are commonly used despite their high flammability or ozone depleting characteristics.     

Sulphurous additives for polystyrene: Influencing decomposition behavior in the condensed phase

The thermal decomposition behaviour of polystyrene (PS) containing sulphur and phosphorus additives was investigated, using thermogravimetry coupled with Fourier transform infrared spectroscopy (TGA‐FTIR). It was found that the additives influence the decomposition process of the polymer in the condensed phase, resulting in a decrease in styrene monomer formation and an increase in styrene oligmer derivatives. Via reference measurements with binary mixtures it was found that the presence of sulphur additives influences the radicalic decomposition process of PS. In combination with quantum chemical calculations it was concluded that this is due to the formation of radicals that abstract hydrogen from the polymer matrix at lower temperatures, disfavouring the radicalic decomposition pathway leading to styrene. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41665.     

Thermally stimulated discharge current studies in pure and fe-doped polystyrene films

Studies were made on the thermally stimulated discharge currents (TSDCs) in pure (undoped) and Fe-doped polystyrene films as a function of polarizing field, polarizing temperature and dopant concentration. While undoped films exhibited a single peak, doped films showed two peaks one at low temperatures and another at high temperatures. The low temperature peak, which exhibits a shift towards lower temperatures with increasing dopant concentration, is attributed to the relaxation of the main chain, while the high temperature peak, which shows a tendency to shift towards higher temperatures with dopant concentration, is due to space charge polarization. The TSDCs were higher for low dopant concentrations than their undoped counterparts, while for high concentrations of the dopant, the TSDCs decreased. Formation of charge transfer complexes at low dopant concentrations and molecular aggregates at higher dopant concentrations are suggested as the possible reasons for this behaviour.     

Supercritical CO2–assisted synthesis and characterization of a polystyrene/thermal polyurethane blend

A blend of polystyrene and thermal polyurethane (PS/TPU) was prepared using supercritical (SC) CO₂ as a substrate‐swelling agent and monomer/initiator carrier. The SC CO₂/styrene/TPU ternary system was studied. Virgin TPU and synthesized blends were characterized through differential scanning calorimetry, infrared spectroscopy, rheometric measurements, and SEM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2016–2020, 2005     

甲烷-四氢呋喃-水体系水合物生成动力学的实验和模型化研究

研究了透明鼓泡塔中含促进剂四氢呋喃（THF）体系中甲烷水合物的生成动力学.分别考察了进气速率、温度、压力、水合物体积分数对甲烷消耗速率的影响.根据Chen-Guo水合物生成机理,采用基础水合物生成反应的量纲1 Gibbs自由焓变-ΔG/RT作为反应的推动力,建立了水合物生成动力学模型,模型中考虑了体系温度、压力和气液接触比表面积的影响.把模型应用于甲烷气体消耗速率的计算,其模型预算结果与实验数据吻合良好,实验结果和反应动力学模型将有助于工业水合反应器的设计和操作条件的设定.     

Experimental study and thermodynamic model for respective solubilities of CO2 and ethanol for CO2‐ethanol‐polystyrene ternary system at elevated pressure and temperature

Foamed non‐Fickian diffusion (FNFD) model for a ternary system was proposed for the first time to regress the desorption data obtained by the gravimetric method. Results showed that FNFD model could accurately describe the diffusion behavior of CO₂ and ethanol out of foamed polystyrene (PS) and well predict total solubilities of CO₂ and ethanol in foamed PS. Meanwhile, Sanchez–Lacombe equation of state (S–L EoS) was adopted to calculate the respective solubilities (solubility of CO₂ in PS or solubility of ethanol in PS) and total solubilities of CO₂ and ethanol in PS for CO₂‐ethanol‐PS ternary system. Results showed that the total solubility of CO₂ and ethanol obtained from S–L EoS agreed well with values obtained by FNFD model. Furthermore, the respective and total solubilities of CO₂ and ethanol at 313.15, 338.15, and 343.15 K were calculated by S–L EoS. Results indicated that in the dissolving process, ethanol would be accelerated by CO₂ to dissolve into PS, and ethanol would compete with CO₂ to dissolve into PS, simultaneously. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46281.