Probing structure–heterogeneous nucleation efficiency relationship of mesoporous particles in polylactic acid microcellular foaming by supercritical carbon dioxide

Heterogeneous nucleating agents that can improve cell morphology of polymer foams have been studied extensively, however, the exact relationship among particle structure, surface modification and nucleating efficiency still remain elusive. Previously, we demonstrated that mesoporous structure benefited nucleating efficiency by comparing solid silica particles and mesoporous particles (MCM-41). Herein, the feasibility of using another type of mesoporous particles, namely, SBA-15 as a nucleating agent for polymer foaming was investigated, but surface modification issue was emphasized. Results reveal that SBA-15 particles show excellent nucleation performance on polylactic acid foaming, and such nucleating effect are dependent on the surface modification. The surface modification using fluorinated silane significantly decreases nucleation energy barrier, and thus shows the highest nucleation efficiency. This work provides a comprehensive insight into structure–nucleating efficiency relationship for mesoporous particles, and highlights the importance of surface modification as a structural factor to optimize the design of effective nucleating agents for polymer foaming.     

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     

超临界CO2制备NaCl/PS微孔泡沫复合材料

利用超临界流体发泡技术制备了氯化钠(NaCl)颗粒填充聚苯乙烯(PS)的微孔泡沫复合材料。通过扫描电子显微镜(SEM)观察了材料的断面形态,并分析了氯化钠的粒径、含量及超临界CO2的饱和温度对微孔泡沫复合材料的泡孔形态的影响。结果表明:含有NaCl颗粒的微孔PS泡沫与纯PS泡沫在泡孔的形状和泡孔的尺寸等方面有所不同,纯PS微孔泡沫材料的泡孔分布较均匀、形状呈椭圆形,而添加了NaCl的PS微孔泡沫出现了大、小泡孔并存的泡孔结构。     

Extruded polystyrene foams with bimodal cell morphology

Extrusion foaming using supercritical carbon dioxide (CO₂) as the blowing agent is an economically and environmentally benign process. However, it is difficult to control the foam morphology and maintain its high thermal insulation comparing to the conventional foams based on fluorocarbon blowing agents. In this study, we demonstrated that polystyrene (PS) foams with the bimodal cell morphology can be produced in the extrusion foaming process using CO₂ and water as co-blowing agents and two particulate additives as nucleation agents. One particulate is able to decrease the water foaming time so both CO₂ and water can induce foaming simultaneously, while the other increases the CO₂ nucleation rate with little effect on the CO₂ foaming time. Our experimental results showed that a dual particulate combination of nanoclay and activated carbon provided the best bimodal structure. The bimodal foams exhibited much better compressive properties and slightly better thermal insulation for PS foams.     

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.     

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     

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.     

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.     

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     

Preparation of low‐density polyethylene foams with high rebound resilience by blending with polyethylene–octylene elastomer

Low‐density polyethylene (LDPE)/polyethylene–octylene elastomer (POE) foams with different composition ratios (POE, cross‐linking agent, and blowing agent) were produced by using the continuous cross‐linking and foaming process to improve the rebound resilience of chemical cross‐linked LDPE foams. The effects of POE, cross‐linking agent, and foaming agent on rebound resilience of LDPE/POE foams were investigated by using a rebound test, cross‐linking degree experiment, differential scanning calorimetry, and scanning electron microscopy. Results show that the rebound resilience of LDPE was improved by increasing the flexibility of cell walls and the cell density and decreasing the foam density. Compared with the rebound resilience of pure LDPE (33%), the proposed LDPE/POE foams could meet the requirements of gymnastics mats for high rebound resilience (55%). POLYM. ENG. SCI., 53:2527–2534, 2013. © 2013 Society of Plastics Engineers     

Extrusion of polystyrene nanocomposite foams with supercritical CO2

Intercalated and exfoliated polystyrene/nano‐clay composites were prepared by mechanical blending and in situ polymerization respectively. The composites were then foamed by using CO₂ as the foaming agent in an extrusion foaming process. The resulting foam structure is compared with that of pure polystyrene and polystyrene/talc composite. At a screw rotation speed of 10 rpm and a die temperature of 200°C, the addition of a small amount (i.e., 5 wt%) of intercalated nano‐clay greatly reduces cell size from 25.3 to 11.1 μm and increases cell density from 2.7 × 10⁷ to 2.8 × 10⁸ cells/cm³. Once exfoliated, the nanocomposite exhibits the highest cell density (1.5 × 10⁹ cells/cm³) and smallest cell size (4.9 μm) at the same particle concentration. Compared with polystyrene foams, the nanocomposite foams exhibit higher tensile modulus, improved fire retardance, and better barrier property. Combining nanocomposites and the extrusion foaming process provides a new technique for the design and control of cell structure in microcellular foams.     

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     

Facile fabrication of superhydrophobic raspberry‐like SIO2/polystyrene composite particles

A facile and novel strategy was reported on the fabrication of raspberry‐like SiO₂/polystyrene (SiO₂/PS) composite particles by emulsion polymerization in the presence of vinyl‐functionalized silica (vinyl‐SiO₂) particles, which were prepared via a one‐step sol–gel process using vinyltriethoxysilane as the precursor. The submicron vinyl‐SiO₂ particles were used as the core, and nanosized PS particles were then adsorbed onto the vinyl‐SiO₂ particles to form raspberry‐like composite particles during the polymerization process. The composition, morphology, and structure of the vinyl‐SiO₂ particles and the SiO₂/PS hybrid particles were characterized by thermogravimetric analysis, nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. Superhydrophobic surface can be constructed by directly depositing the raspberry‐like SiO₂/PS composite particles on glass substrate, and the water contact angle can be adjusted by the styrene/SiO₂ weight ratio. In addition, the superhydrophobic film possessed a strong adhesive force to pin water droplet on the surface even when the film was turned upside down. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

SBA-15形貌对聚乳酸微孔发泡的影响

文章采用水热法合成了球状、棒状与环状三种形貌的SBA-15无机介孔粒子,利用含氟硅烷对粒子进行亲二氧化碳修饰后,用于聚乳酸超临界二氧化碳(scCO2)微孔发泡,探索了粒子形貌对聚乳酸发泡材料的泡孔结构的影响。TG,BET和SEM等分析表明,不同粒子形貌的介孔粒子具有不同的硅烷接枝率,在聚乳酸微孔发泡材料中异相成核作用也不同,就泡孔尺寸和泡孔密度来讲,环状SBA-15粒子对聚乳酸发泡的异相成核作用最好,表明介孔粒子有望成为新型的微孔发泡成核剂。     

Synthesis of iron oxides intercalated montmorillonite and α‐zirconium phosphate particles and their applications in polystyrene composites

Three kinds of particles of organically modified montmorillonite (OMT) intercalated with iron oxides (Fe‐OMT), hexadecyltrimethylammonium bromide (CTAB) and ethylamine (EA)‐modified zirconium phosphate (ZrP) intercalated with iron oxides, named as Fe‐ZrP(CTAB) and Fe‐ZrP(EA), respectively, were synthesized through a simple route. Characterization of these particles showed that they had a mesoporous lamellar structure with high specific surface area and mesoporous volume. The influence of these particles on the thermal properties and combustion effluents of polystyrene (PS) were comparatively studied with the widely used OMT. The results suggested that the presence of Fe‐OMT, Fe‐ZrP(CTAB), and Fe‐ZrP(EA) imparted PS with an increased thermal degradation onset temperature and a higher glass transition temperature, but they could not increase the thermo‐oxidative stability remarkably as OMT did. Meanwhile, Fe‐ZrP(CTAB) and Fe‐ZrP(EA) exhibited stronger acidity and higher efficiency in preventing the condensed phase oxidation than either OMT or Fe‐OMT, since they imparted the PS composites with a higher ratio of CO/CO₂ in the combustion effluents. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42737.     

Polypropylene‐dispersed domain as potential nucleating agent in PS and PMMA solid‐state foaming

The potential of using dispersive domains in a polymer blend as a bubble nucleating agent was investigated by exploiting its high dispersibility in a matrix polymer in the molten state and its immiscibility in the solid state. In this experiments, polypropylene (PP) was used as the nucleating agent in polystyrene (PS) and poly(methyl methacrylate) (PMMA) foams at the weight fraction of 10, 20, and 30 wt %. PP creates highly dispersed domains in PS and PMMA matrices during the extrusion processing. The high diffusivity of the physical foaming agent, i.e., CO₂ in PP, and the high interfacial tension of PP with PS and PMMA could be beneficial for providing preferential bubble nucleation sites. The experimental results of the pressure quench solid‐state foaming of PS/PP and PMMA/PP blends verified that the dispersed PP could successfully increase the cell density over 10⁶ cells/cm³ for PS/PP and 10⁷ cells/cm³ for PMMA/PP blend and reduce the cell size to 24 μm for PS/PP and 9 μm for PMMA/PP blends foams. The higher interfacial tension between PP and the matrix polymer created a unique cell morphology where dispersed PP particles were trapped inside cells in the foam. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of polystyrene particles with different morphologies

Micron‐sized, cross‐linked polystyrene (PS) particles with different morphologies were prepared by the developed dispersion polymerization. By scanning electron microscope (SEM) observation, it was found that these PS particles had interesting shapes such as deformed sphere, hollow hemisphere and spheroid‐like shape when initial monomer concentration, reaction time, and temperature and addition way of the reagent added in the third stage were different. The shape of the PS particles was changed from hollow hemisphere to spheroid‐like shape with prolongation of the reaction time. It was remarkable that the rough surface of hollow‐hemisphere‐like PS particles became smooth and the hollow structure of smooth‐hollow‐hemisphere‐like PS particles grew into solid structure at the same time. The formation mechanism behind these phenomena was discussed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Long‐term thermal conductivity of cyclopentane–water blown rigid polyurethane foams reinforced with different types of fillers

An understanding of the long‐term thermal conductivity of rigid polyurethane (RPU) foams presents great interest in the building field considering the conservation of energy efficiency. In this study, the effect of different types of particles (talc, diatomaceous earth and non‐porous silica) on the thermal conductivity of RPU foams blown with cyclopentane and water as blowing agents was investigated during 3 years of aging. The characterization of the cellular structure shows how the addition of particles causes a cell size reduction of the foams, and consequently an enhancement of the thermal properties just after production. However, this initial reduction is not maintained, because each foam shows a different thermal conductivity evolution with time. We have found, for the first time, a relationship between the slope of the thermal conductivity versus time at the first measurements and the internal temperature reached during the foaming process. The evolution of the RPU foams in which higher internal temperatures were reached is more pronounced than in those RPU foams where lower foaming temperatures were observed. This effect is related to the kinetics of the diffusion of the gas occluded inside the cells and imposes a new criterion for the selection of particles to reduce the thermal conductivity of RPU foams; these additives should ideally decrease the temperature reached during the foaming process. Moreover, the effect of aging on the thermal conductivity is explained by using theoretical models. © 2019 Society of Chemical Industry     

超临界CO_2发泡聚苯乙烯工艺研究

以超临界CO_2为发泡剂,采用釜压法在不同发泡工艺条件下制备了聚苯乙烯(PS)发泡试样,通过扫描电子显微镜对PS发泡试样的泡孔形貌进行了表征,探讨了不同发泡工艺对PS发泡试样发泡性能的影响。结果表明,随发泡温度的升高,PS发泡试样泡孔尺寸增大,泡孔密度下降,而泡沫密度呈现先降低后升高的趋势,发泡倍率与此相反;增大保压时间和保压压力,可提高试样的发泡效果。当发泡温度为136℃,保压压力为20 MPa,保压时间为4 h时,PS发泡试样的发泡效果最好,其泡沫密度为0.043 g/cm~3,发泡倍率为24.4,泡孔尺寸为59.8μm,泡孔密度为6.20×107个/cm~3。     

Effect of the chemical characteristics of mesoporous silica MCM‐41 on morphological,thermal, and rheological properties of composites based on polystyrene

Mesoporous silica nanoparticles (MCM‐41) with an average diameter of ～ 20 nm were synthesized by a sol‐gel method using binary surfactant system. Polystyrene (PS) composites containing mesoporous silica nanoparticles were prepared by in situ polymerization of styrene monomers. Similar in situ polymerized PS composites were prepared based on the modified silica functionalized with methyl and vinyl groups. The effects of silylation on thermal and rheological properties of the PS/silica composites are investigated. Of particular importance is that the in situ polymerization of monomers within the mesoporous silica may trap some polymer chains, if not all, thereby affording a greater physical interaction between polymer and the porous fillers, whereas the chemical modification of silica surface promotes the polymer–filler interaction, which in turn enhances the thermal stability of composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009