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     

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.     

Physical extruder foaming of poly(lactic acid)—processing and foam properties

The article describes extrusion foaming of poly(lactic acid) (PLA) using carbon dioxide in the supercritical state as foaming agent emphasizing the steps required to establish a stable extrusion process. Low melt strength of PLA plays a role in optimizing processing conditions. The tests included PLA grades of different viscosity in addition to a chain extender. Processing at low temperature is possible due to the plasticizing effect of the CO₂ on the PLA melt and a sufficiently low melt temperature is also a prerequisite in production of stable foams due to improved melt strength. Foams were characterized by density, cell structure, crystallinity, and mechanical properties in compression. Low density, microcellular foams with density down to 20–30 kg/m³ were obtained for three different PLA grades. Varying die temperature and pressure drop rate we can explain observed abrupt drops in density with increasing CO₂ content by the interplay between cell nucleation and gas diffusivity at given temperatures. An effect on melt strength similar to using a chain extender is achieved by lowering the melt temperature at the die. Observed variations in sample crystallinity do not correlate with foam density. The PLA foams have good energy absorption capability. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Supercritical CO2-assisted extrusion foaming: A suitable process to produce very lightweight acrylic polymer micro foams

A strategy of CO₂-assisted extrusion foaming of PMMA-based materials was established to minimize both foam density and porosities dimension. First a highly CO₂-philic block copolymer (MAM: PMMA-PBA-PMMA) was added in PMMA in order to improve CO₂ saturation before foaming. Then the extruding conditions were optimized to maximize CO₂ uptake and prevent coalescence. The extruding temperature reduction led to an increase of pressure in the barrel, favorable to cell size reduction. With the combination of material formulation and extruding strategy, very lightweight homogeneous foams with small porosities have been produced. Lightest PMMA micro foams (ρ = 0.06 g cm⁻³) are demonstrated with 7 wt% CO₂ at 130°C and lightest blend micro foams (ρ = 0.04 g cm⁻³) are obtained at lower temperature (110°C, 7.7 wt% CO₂). If MAM allows a reduction of T^foaming, it also allows a much better cell homogeneity, an increase in cell density (e.g., from 3.6 10⁷ cells cm⁻³ to 2 to 6 10⁸ cells cm⁻³) and an overall decrease in cell size (from 100 to 40 μm). These acrylic foams produced through scCO₂-assisted extrusion has a much lower density than those ever produced in batch (ρ ≥ 0.2 g cm⁻³).     

Batch foaming of carboxylated multiwalled carbon nanotube/poly(ether imide) nanocomposites: The influence of the carbon nanotube aspect ratio on the cellular morphology

A series of microcellular poly(ether imide) (PEI) foams and nanocellular carboxylated multiwalled carbon nanotube (MWCNT‐COOH)/PEI foams were prepared by the batch foaming method. MWCNT‐COOHs with different aspect ratios were introduced into the PEI matrix as heterogeneous nucleation agents to improve the cell morphology of the microcellular PEI foams. The effect of the aspect ratio of the MWCNT‐COOHs on the cellular morphology, and gas diffusion is discussed. The results show that with the addition of MWCNT‐COOH, the sorption curve showed a slight reduction of carbon dioxide solubility, but the gas diffusion rate could be improved. The proper aspect ratio of MWCNT‐COOH could improve the cellular morphology under the same foaming conditions, in which m‐MWCNT‐COOH (aspect ratio ≈ 1333) was the best heterogeneous nucleation agent. When the foaming temperature was 170°C, the cell size and cell density of nanocellular m‐MWCNT‐COOH reduced to 180 nm and increased to 1.58 × 10¹³ cells/cm³, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42325.     

Effect of solvent plasticization on polypropylene microcellular foaming process and foam characteristics

In this research, the effect of crystalline fraction of polypropylene (PP) on cell nucleation behavior was overcome by an introduction of solvent‐plasticized step to the microcellular foaming in a solid‐state batch‐foaming process. Utilizing the plasticization performance of the solvent facilitated the PP to be foamed at the temperatures lower than its melting point with the dramatic development in the cellular morphology of the final foams. In consequence of the heterogeneous cell nucleation sites induction and the crystalline loss, which were induced by solvent, a high cell density (i.e., 10⁹–10¹⁰ cells/cm³) was promoted without the cell sacrificing at the elevated temperatures (155 and 165°C) and favorable PP microcellular foams were accomplished. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of processing parameters and thermal history on microcellular foaming behaviors of PEEK using supercritical CO2

In this study, we mainly investigate the solid‐state foaming of polyether ether ketone (PEEK) with different crystallinities using supercritical CO₂ as a physical blowing agent. The gaseous mass‐transfer and thermophysical behaviors were studied. By altering the parameters of the foaming process, microcellular foams with different cell morphologies were prepared. The effect of crystallization on the cell morphology was also investigated in detail. The results indicate that the crystallization restricts gas diffusion in the material, and the thermophysical behaviors of the saturated PEEK sample with low crystallinity presents two cold crystallization peaks. The cell density decreases and the cell size increases as the saturation pressure increases. The cell density of the microcellular foams prepared under 20 MPa is 1.23 × 10¹⁰ cells/cm³, which is almost 10 times compares to that under 8 MPa. The cell size increases as the foaming time extends or the foaming temperature increases. It is interesting that the cell morphology with a bimodal cell‐size distribution is generated when the samples are foamed at temperatures higher than 320°C for a sufficient time. Additionally, nanocellular foams can be obtained from a highly crystallized PEEK after the decrystallization process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42576.     

Foaming behavior of microcellular foam polypropylene/modified nano calcium carbonate composites

A new process was used to prepare microcellular foams with supercritical carbon dioxide as the physical foaming agent in a batch. The foaming temperature range of the new process was about five times broader than that of the conventional one. Characterization of the cellular structure of the original polypropylene (PP) and PP/nano‐CaCO₃ (nanocomposites) foams was conducted to reveal the effects of the blend composition and processing conditions. The results show that the cellular structure of the PP foams was more sensitive to the foaming temperature and saturation pressure variations than that of the nanocomposite foams. Uniform cells of PP foams are achieved only at a temperature of 154°C. Also, the low pressure of 20 MPa led to very small cells and a low cell density. The competition between the cell growth and cell nucleation played important role in the foam density and was directly related to the foaming temperature. Decreasing the infiltration temperature depressed the initial foaming temperature, and this resulted in significantly larger cells and a lower cell density. A short foaming time led to a skin–core structure; this indicated that a decrease in the cell size was found from skin to core, but the skin–core structure gradually disappeared with increasing foaming time. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A conductive foam: Based on novel poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer filled by carbon black

In this article, a conductive foam based on a novel styrene‐based thermoplastic elastomer called poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer S(BS)S was prepared and introduced. S(BS)S was particularly designed for chemical foaming with uniform fine cells, which overcame the shortcomings of traditional poly(styrene‐b‐butadiene‐b‐styrene) tri‐block copolymer (SBS). The preparation of conductive foams filled by the carbon black was studied. After the detail investigation of cross‐linking and foaming behaviors using moving die rheometer, the optimal foaming temperature was determined at 180°C with a complex accelerator for foaming agent. Scanning electron microscopy (SEM) images shown that the cell bubbles of conductive foam were around 30–50 µm. The conductivity of foams was tested using a megger and a semiconductor performance tester. SEM images also indicated that the conductivity of foams was mainly affected by the distribution of carbon black in the cell walls. The formation of the network of the carbon black aggregates had a contribution to perfect conductive paths. It also found that the conductivity of foams declined obviously with the foaming agent content increasing. The more foaming agent led to a sharp increasing of the number of cells (from 2.93 × 10⁶ to 6.20 × 10⁷ cells/cm³) and a rapid thinning of the cell walls (from 45.3 to 1.4 µm), resulting in an effective conductive path of the carbon black no forming. The conductive soft foams with the density of 0.48–0.09 g/cm³ and the volume resistivity of 3.1 × 10³?2.5 × 10⁵ Ω cm can be easily prepared in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41644.     

Effects of formulation and processing parameters on the morphology of extruded polypropylene‐(waste ground rubber tire powder) foams

This paper presents an experimental study of the foaming behavior of polypropylene (PP)/(waste ground rubber tire powder) (WGRT) blends when using a chemical blowing agent in an extrusion foaming process. The effects of formulations (i.e., WGRT content, blowing agent content, compatibilizer) and the processing parameters (i.e., die temperature, screw speed) on the void fraction, average cell size, cell density, and cell morphology of the PP/WGRT foams were investigated. The blowing agent loading affected the cell structure of the foams and the average cell size, and the void fraction increased with increasing blowing agent loading. Both increasing the screw speed and decreasing the die temperature could establish a high pressure drop in the extruder die, and these were beneficial to the foaming extrusion. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Study of microcellular foaming of polystyrene aided with 45 kHz of ultrasound waves energy

ABSTRACT

In the microcellular foam plastic processing, cellular formation stage was being an essential stage since the nucleation and growth of the cell take place within. Based on classical nucleation theory, diminution of the free energy for nucleation, exponentially lead to an increase in the nucleation rate. This can be done by increasing the super-saturation level which achieved by heating the gas-saturated polymer. Hence, the advance is taken out by utilizing the ultrasound wave simultaneously with heating for foaming Polystyrene-scCO₂, which, not only to keep the super-saturation degree but also reduce the nucleation barrier. In this work, foaming was conducted under 45 kHz of ultrasound and varying the foaming temperature after saturating polystyrene with scCO₂. The results demonstrate, that foaming under ultrasound, the expansion ratio attained up to 1.5 fold, increase along with the heating temperature. Higher cell densities obtained with ultrasound applied at 50°C, however only slight difference can be seen, which about 10¹⁰–10¹¹ cell/cm³. From the cell size distribution results, cell distributed around 0.5–3.5 µm, with or without ultrasound applied for 60 and 70°C, Meanwhile at 50°C of foaming, the lowest cell size obtained with the aid of ultrasound in the range of 0.3–2.4 µm.     

Effect of glass transition temperature and saturation temperature on the solid‐state microcellular foaming of cyclic olefin copolymer

Effect of glass transition temperature and saturation temperature on the solid‐state microcellular foaming of cyclic olefin copolymer (COC)—including CO₂ solubility, diffusivity, cell nucleation, and foam morphology—were investigated in this article. COCs of low T_g (78°C) and high T_g (158°C) were studied. Solubilities are 20–50% higher in high T_g COC than in the low T_g COC across the saturation temperature range. Diffusivities are about 15% higher on average in high T_g COC for temperatures up to 50°C. A much faster increase of diffusivity beyond 50°C is observed in low T_g COC due to it being in the rubbery state. Under similar gas concentration, high T_g COC starts foaming at a higher temperature. And the foam density decreases faster in low T_g COC with foaming temperature. Also, high T_g COC foams show about two orders of magnitude higher cell nucleation density than the low T_g COC foams. The effect of saturation temperature on microcellular foaming can be viewed as the effect of CO₂ concentration. Nucleation density increases and cell size decreases exponentially with increasing CO₂ concentration. Uniform ultramicrocellular structure with an average cell size of 380 nm was created in high‐T_g COC. A novel hierarchical structure composed of microcells (2.5 μm) and nanocells (cell size 80 nm) on the cell wall was discovered in the very low‐density high‐T_g COC foams. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42226.     

木塑/超临界流体复合材料泡孔成核的数值模拟研究

以木塑/超临界二氧化碳（WPC/Sc-CO2）复合材料为研究对象,采用有限元分析软件Polyflow对不同尺寸的挤出发泡机头内的流场进行数值模拟,研究机头尺寸对WPC/Sc-CO2复合材料泡孔成核的影响。结果表明,增加挤出发泡机头内毛细管段长度对机头内压力降速率和泡孔成核点距离机头出口的位置影响很小;而减小挤出发泡机头内毛细管段直径可增加机头内压力降速率,同时使泡孔成核点的位置更靠近机头出口。     

Open-celled microcellular foaming and the formation of cellular structure by a theoretical pattern in polystyrene

An open-celled structure was produced using polystyrene and supercritical carbon dioxide in a novel batch process. The required processing conditions to achieve open-celled structures were predicted by a theoretical model and confirmed by the experimental data. The theoretical model predicts that at least a saturation pressure of 130 bar and a foaming time between 9 and 58 s are required for this system to produce an open-celled structure. The foaming temperature range has been selected to be higher than the polymer glass transition temperature yet not higher than a temperature limit where the gas starts leaving the system. The experimental results in the batch foaming process verified the model substantially. The SEM pictures showed the presence of pores between the cells, and the mercury porosimetry test results verified the overall open-celled structure. Experimental results also showed that by increasing the saturation pressure and the foaming temperature, there was a drop in the time required for open-celled structure formation. At saturation pressure of 130 bar, foaming temperature of 150 °C and a foaming time of 60 s, open-celled microcellular polystyrene foams were obtained using supercritical CO₂ in the batch process. Based on the results, a schematic diagram, depicting the process of foam structure formation from nucleation to bubble coalescence and gas escape from polymer, was proposed. Theoretical calculations showed that by increasing foaming time, cell size was increased and cell density was reduced and the experimental results verified this prediction.     

Manufacture of rigid PVC/wood‐flour composite foams using moisture contained in wood as foaming agent

Relatioships between the density of foamed rigid PVC/wood‐flour composites and the moisture content of the wood flour, the chemical foaming agent (CFA) content, the content of all‐acrylic foam modifier, and the extruder die temperature were determined by using a response surface model based on a four‐factor central composite design. The experimental results indicated that there is no synergistic effect between teh CFA content and the moisture content of the wood flour. Wood flour moisture could be used effectively as foaming agent in the production of rigid PVC/wood‐flour composite foams. Foam density as low as 0.4 g/cm³ was produced without the use of chemical foaming agents. However, successful foaming of rigid PVC/wood‐flour composite with moisture contained in wood flour strongly depends upon the presence of all‐acrylic foam modifier in the formulation and the extrusion die temperature. The lowest densities were achieved when the all‐acrylic foam modifier concentration was between 7 phr and 10 phr and extruder die temperature was as low as 170°C.     

Role of chain extension in the rheological properties,crystallization behaviors,and microcellular foaming performances of poly (butylene adipate-co-terephthalate)

Currently, the fabrication of microcellular semicrystalline polymer foam using supercritical CO₂ as a blowing agent constitutes a worldwide interest. In this work, a facile approach of chain extension and batch foaming was proposed to prepare microcellular semicrystalline poly (butylene adipate-co-terephthalate) (PBAT) foam using CO₂ as a physical blowing agent. With the introduction of chain extender (CE), the weight-average molecular weight and gel fraction of PBAT samples increased; their crystallization temperature increased from 74.2 to 86.9 °C and their viscoelasticity was improved greatly. Microcellular PBAT foams with the cell size <4 μm and the cell density more than 10¹⁰ cells cm⁻³ were fabricated successfully. With increasing concentration of CE, the cell density and volume expansion ratio (VER) of various PBAT foams increased from 3.4 × 10¹⁰ to 8.7 × 10¹⁰ cells cm⁻³ and from 1.5 to 2.0 times, respectively. With increasing foaming temperature, the cell size and VER increased and the cell density decreased. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47322.     

Use of Nitrogen as a Blowing Agent for the Production of Fine‐Celled High‐Density Polyethylene Foams

Summary: While many experiments have been performed to examine the effects of administering CO₂ as a blowing agent in the foaming process, very few studies have investigated the use of N₂ for this purpose. In this study, foaming experiments were conducted in extrusion using HDPE as a polymeric material and N₂ as a blowing agent. Talc was used as a nucleating agent, and three different pressure‐drop rates were applied to study the effects of pressure‐drop rates on HDPE foams. The experimental results revealed that the void fraction of high‐density foams blown with N₂ was not affected by the die temperature, contrasting the situation in low‐density foams. Surprisingly, it was the cell density which determined the void fraction of high‐density foams. It was also found that the use of talc significantly increased the cell density and the void fraction of the foams and minimized the role played by the pressure‐drop rate in cell nucleation.

Effect of N₂ content on the cell density of HDPE foams.     

Investigation of the effect of foaming process parameters on expanded thermoplastic polyurethane bead foams properties using response surface methodology

Expanded thermoplastic polyurethane (ETPU) bead foams were fabricated by batch foaming with supercritical CO₂ as blowing agent. On the basis of single factor investigation, the response surface methodology based on Box‐Behnken Design was used to investigate the influences of saturation pressure, temperature, and soaking time and their interactions on foaming behavior of ETPU. The results showed that saturation temperature was the most significant parameter affecting the expansion ratio, shrinkage ratio, and cell morphology of ETPU. Moreover, there was an interaction effect between saturation temperature and soaking time, wherein the expansion ratio of ETPU was more sensitive to change of soaking time at higher temperature. As the soaking time increased, the shrinkage of ETPU increased firstly and then leveled off, and the cell diameter decreased significantly. By applying the response surface methodology optimization, ETPU bead foams with final expansion ratio of 8.04, mean cell diameter of 74.2 μm, and average cell density of 1.46 × 10⁷cell/cm³ can be obtained while the optimum conditions at saturation pressure of 15 MPa, saturation temperature of 100 °C and soaking time for 60 min. In addition, the dual melting peak of ETPU characteristics demonstrated that it is suitable for steam‐chest molding technology. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46327.     

Foam Processing and Cellular Structure of Polycarbonate‐Based Nanocomposites

Summary: Via a batch process in an autoclave, foam processing of intercalated PC/clay nanocomposites, having different amounts of clay, has been conducted using supercritical CO₂ as a foaming agent. The cellular structures obtained from various foaming temperature‐CO₂ pressure ranges were investigated by SEM. The incorporation with nanoclay‐induced heterogeneous nucleation occurs because of a lower activation energy barrier compared with homogeneous nucleation as revealed by the characterization of the interfacial tension between bubble and matrix. The controlled structure of the PCCN foams changed from microcellular (d ? 20 µm and N_c ? 1.0 × 10⁹ cells · cm^?3) to nanocellular (d ? 600 nm and N_c ? 3.0 × 10¹³ cells · cm^?3). The mechanical properties of PCCN foams under compression test were discussed.

TEM micrograph for the structure of the cell wall foamed at 160 °C.     

A strategy for the preparation of closed‐cell and crosslinked polypropylene foam by supercritical CO2 foaming

We report the preparation of a closed‐cell polypropylene (PP) foam material by supercritical carbon dioxide foaming with the assistance of γ‐ray radiation crosslinking. Styrene–ethylene–butadiene–styrene (SEBS) copolymer was added to PP to enhance radiation crosslinking and nucleation. Radiation effects on the foaming of the PP/SEBS blend with different ratios were investigated. A significant improvement in the foaming of the crosslinked PP/SEBS blend was achieved as compared to pristine PP. The cell density of the crosslinked PP/SEBS foam greatly increased at a dose of 10 kGy and a high closed‐cell ratio was obtained. The tensile strength of the crosslinked PP/SEBS foams (10 kGy) was improved from 14 to 20.7 MPa compared to pristine PP foam (0 kGy). In addition, the crosslinked PP/SEBS blend exhibited a wider foaming temperature window (10 °C) as compared to the non‐crosslinked ones (4 °C). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45809.