The effects of nanoclay on the extrusion foaming of wood fiber/polyethylene nanocomposites

This article presents the foaming behaviors of wood fiber/high density polyethylene (HDPE) composites with small amounts of nanoclay. Melt compounding is used to prepare two types of clay‐filled wood fiber composites: intercalated and exfoliated clay composites. Their respective morphologies are determined using wide‐angle X‐ray diffraction (XRD) and transmission electron microscopy (TEM). We subsequently conduct an extrusion foaming experiment of the composites using N₂ as the blowing agent. Varying the wood fiber content, as well as the processing parameters, such as temperature and pressure, the effects of different amounts of clay and the degree of exfoliation on the final cell morphology and the foam density of the wood fiber/HDPE/clay nanocomposite foams are studied. The results suggested that the addition of nanoclay improved the cell morphology of the wood fiber/HDPE composite foams as its content and degree of dispersion increased. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effects of clay dispersion on the foam morphology of LDPE/clay nanocomposites

Intercalated and exfoliated low‐density polyethylene (LDPE)/clay nanocomposites were prepared by melt blending with and without a maleated polyethylene (PE‐g‐MAn) as the coupling agent. Their morphology was examined and confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of clay content and dispersion on the cell morphology of nanocomposite foams during extrusion foaming process were also thoroughly investigated, especially with a small amount of clay of 0.05–1.0 wt%. This research shows the optimum clay content for achieving microcellular PE/clay nanocomposite foams blown with supercritical CO₂. It is found that < 0.1 wt% of clay addition can produce the microcellular foam structure with a cell density of > 10⁹ cells/cm³ and a cell size of ～ 5 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2129–2134, 2007     

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     

Effect of acetylated cellulose nanocrystals on solid-state foaming behaviors of chain-extended poly(butylene adipate-co-terephthalate)

Fully biodegradable chain-extended poly(butylene adipate-co-terephthalate) (CPBAT)/acetylated cellulose nanocrystals (ACNCs) nanocomposites were prepared by the melt compounding process. The dispersibility of CNCs in deionized water was improved through the surface acetylation, which was observed by atomic force microscope and transmission electron microscope. The chain extender was added to the PBAT matrix to improve the melt strength and viscoelasticity of PBAT. The ACNC nanoparticles which served as bionano-reinforcing fillers were introduced into CPBAT to further improve the crystallization behaviors and rheological properties of CPBAT/ACNCs nanocomposites. Finally, the CPBAT/ACNCs nanocomposite foams were prepared via batch supercritical CO₂ foaming process. The cell structure and morphology of various CPBAT/ACNCs foams were investigated by scanning electron microscope. It was found that the introduction of ACNC nanoparticles led to a reduction of cell size, an increase in cell density and in the uniform cell distribution owing to the heterogeneous cell nucleation effect of ACNCs. Meanwhile, the volume expansion ratio (VER) of CPBAT foams reached to 9.21 times, the highest VER reported for PBAT foam in the current literature. Also, the thermal conductive properties of nanocomposites and foams also were studied by a laser thermal conductivity analyzer.     

Batch foaming of SAN/clay nanocomposites with scCO2: A very tunable way of controlling the cellular morphology

This paper aims at elucidating some important parameters affecting the cellular morphology of poly(styrene-co-acrylonitrile) (SAN)/clay nanocomposite foams prepared with the supercritical CO₂ technology. Prior to foaming experiments, the SAN/CO₂ system has first been studied. The effect of nanoclay on CO₂ sorption/desorption rate into/from SAN is assessed with a gravimetric method. Ideal saturation conditions are then deduced in view of the foaming process. Nanocomposites foaming has first been performed with the one-step foaming process, also called depressurization foaming. Foams with different cellular morphology have been obtained depending on nanoclay dispersion level and foaming conditions. While foaming at low temperature (40 °C) leads to foams with the highest cell density (∼10¹²-10¹⁴ cells/cm³), the foam expansion is restricted (d∼0.7-0.8 g/cm³). This drawback has been overcome with the use of the two-step foaming process, also called solid-state foaming, where foam expansion occurs during sample dipping in a hot oil bath (d∼0.1-0.5 g/cm³). Different foaming parameters have been varied, and some schemes have been drawn to summarize the characteristics of the foams prepared - cell size, cell density, foam density - depending on both the foaming conditions and nanoclay addition. This result thus illustrates the huge flexibility of the supercritical CO₂ batch foaming process for tuning the foam cellular morphology.     

Polypropylene–nano‐silica nanocomposite foams: mechanisms underlying foamability,and foam microstructure,crystallinity and mechanical properties

We investigate the production and characterization of foams prepared from polypropylene (PP) as well as PP–silica nanocomposites containing different loadings of nano‐silica. This study was carried out to investigate the mechanisms underlying the production of foams with a regular cell structure through the use of nano‐scale fillers. Foaming was carried out in batch mode using an autoclave with CO₂ as the physical blowing agent; high pressures of the order of 14 MPa were achieved through a combination of active pressurization and the use of high foaming temperatures. The resulting PP nanocomposite foams were characterized in detail to quantify the effect of the nano‐silica loading on the foam density and mechanical, morphological and thermal properties. The addition of nano‐silica in PP resulted in the improvement of foam quality – as assessed from the well‐defined and regular cell structures with absence of cell coalescence – as well as an increase in expansion ratio and decrease in foam density. Careful analyses of trends in cell size, cell density and expansion ratio of the foams were correlated with measurements of melt rheology and nano‐filler morphology of the unfoamed specimens in order to identify subtle details regarding the role of silica nanoparticles in improving foam quality. © 2019 Society of Chemical Industry     

An experimental and theoretical investigation of the compressive properties of multi-walled carbon nanotube/poly(methyl methacrylate) nanocomposite foams

Polymer nanocomposite foams are promising low density substitutes for nanocomposites. Carbon nanotube/polymer nanocomposite foams possess high strength, low density, and can be made conductive. Good control of foam properties is of great importance in the application of such materials. In the current study, multi-walled carbon nanotubes (MWNTs) with controlled aspect ratio were used to alter the foam morphology in MWNT/poly(methyl methacrylate) (PMMA) nanocomposite foams produced by a supercritical carbon dioxide (CO₂) foaming process. It was found that with the addition of one weight percent of MWNTs, the Young’s modulus of polymer foams increased by as much as 82%, and the collapse strength increased by as much as 104%. The influence of MWNT aspect ratio on the compressive properties of nanocomposite foams was investigated. The addition of MWNTs influenced the foam properties in two ways: improving the compressive properties of the solid matrix, and reducing the bubble size of the nanocomposite foams. A modified constitutive model for predicting the compressive properties of high density closed-cell polymer foams was developed. The influence of the bubble size on the mechanical properties of polymer foams was discussed based on the new model.     

Synthesis and processing of PMMA carbon nanotube nanocomposite foams

Poly(methyl methacrylate) (PMMA) multi-walled carbon nanotubes (MWCNTs) nanocomposites were synthesized by several methods using both pristine and surface functionalized carbon nanotubes (CNTs). Fourier transform infrared (FTIR) spectroscopy was used to characterize the presence and types of functional groups in functionalized MWCNTs, while the dispersion of MWCNTs in PMMA was characterized using scanning electron microscopy (SEM). The prepared nanocomposites were foamed using carbon dioxide (CO₂) as the foaming agent. The cell morphology was observed by SEM, and the cell size and cell density were calculated via image analysis. It was found that both the synthesis methods and CNTs surface functionalization affect the MWCNTs dispersion in the polymer matrix, which in turn profoundly influences the cell nucleation mechanism and cell morphology. The MWCNTs are efficient heterogeneous nucleation agents leading to increased cell density at low particle concentrations. A mixed mode of nucleation mechanism was observed in nanocomposite foams in which polymer rich and particle rich region co-exist due to insufficient particle dispersion. This leads to a bimodal cell size distribution. Uniform dispersion of MWCNTs can be achieved via synergistic combination of improving synthesis methodology and CNTs surface functionalization. Foams from these nanocomposites exhibit single modal cell size distribution and remarkably increased cell density and reduced cell size. An increase in cell density of ∼70 times and reduction of cell size of ∼80% was observed in nanocomposite foam with 1% MWCNTs.     

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.     

A simple method for preparation of polymer microcellular foams by in situ generation of supercritical carbon dioxide from dry ice

In this work, poly(methyl methacrylate) (PMMA) and PMMA/nanoclay nanocomposite microcellular foams were successfully prepared using a simple method based on in situ generation of supercritical carbon dioxide (CO₂) from dry ice. The method was compared with conventional methods exempted from high pressure pump and a separate CO₂ tank. Effect of various processing conditions such as saturation temperature and pressure and clay concentration on cellular morphology and hardness of the prepared microcellular foams was examined. State of the clay dispersion in the prepared PMMA/clay nanocomposites was characterized using X-ray diffraction and transmission electron microscopy techniques. Field emission scanning electron microscopy was used to study cellular morphology of the prepared foams. It was observed that elevation of saturation temperature from 85 to 105 °C at constant saturation pressure increased cell density and decreased average cell size of the prepared PMMA foams. Furthermore, an increase in saturation pressure from 120 to 180 bar resulted in a reduction in average cell diameter and an increase in cell density of the prepared PMMA foams. On the basis of the gathered results, optimum conditions for preparation of PMMA microcellular foams were determined and applied for preparation of PMMA/nanoclay microcellular foams. It was shown that incorporation of clay into the polymer matrix resulted in a finer and more uniform cellular morphology in the final microcellular foams. It was also observed that incorporation of nanoclay into the prepared foams, up to 3 wt%, led to a moderate increase in the foam hardness.     

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。     

Effects of multi‐walled carbon nanotube functionalization on the morphological and mechanical properties of nanocomposite foams based on poly(vinyl chloride)/(wood flour)/ (multi‐walled carbon nanotubes)

Experimental results are presented for nanocomposite foams based on unplasticized poly(vinyl chloride)/(wood flour)/(multi‐wall carbon nanotubes) (PVC/WF/MWCNTs). The nanocomposite samples were prepared in an internal mixer and foamed via a batch processing method using compression molding. Nanoparticles were functionalized by sodium hypochlorite solution, and the functionalization process was monitored by Fourier‐transform infrared spectroscopy. The effects of MWCNTs (both neat and functionalized) and blowing agent concentration on the morphological properties (cell size and cell density) and mechanical properties (tensile and flexural strength) of the foam samples were studied. The results revealed that foam cell sizes decreased and cell densities increased with addition of MWCNTs. The dispersion of nanoparticles in the PVC medium was increased by functionalization, and the morphological properties of the foams containing functionalized nanoparticles were improved. Density of nanocomposite foams decreased more with functionalized MWCNTs as compared to other samples. Chemical blowing agent concentration had no significant effect on sample density. Mechanical properties of the samples were improved by using functionalized MWCNTs in comparison with those of foams without this component. J. VINYL ADDIT. TECHNOL., 18:161–167, 2012. © 2012 Society of Plastics Engineers     

Effect of clay dispersion on the cell structure of LDPE/clay nanocomposite foams

In this study, the effect of clay and its dispersion state on the cell morphology and foaming behavior of chemically crosslinked polyethylene (PE) foams were examined. In addition, the effect of foaming process on the clay morphology was also considered. It was shown that the morphology of the clay before the foaming process and its compatibility with PE matrix play a major role in determining the final foam properties. A PE‐g‐MA compatibilizer was used to increase the melt intercalation of PE onto the clay galleries and to improve clay dispersion in the PE matrix. The uniform dispersion of clay provided greater and well‐ dispersed nucleation sites. This led to smaller cell size, narrower cell size distribution, and higher cell density, and lower foam density. During the foaming process, intercalated clays were delaminated due to the rapid polymer melt expansion that inhibited gas release and increased foam expansion ratio. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effect of nanoparticles orientation on morphology of polymeric nanocomposite foams: preparation of foamed nanocomposite fibers by supercritical carbon dioxide

ABSTRACT

Polymeric foams have received increasing attention in both academic and industrial communities. Using of nanoparticles as heterogeneous nucleation agent has been verified as one of the most valid means to enhance cell nucleation and improve cell morphology. However, few researches have been conducted to investigate the effect of the nanoparticles’ spatial orientation on their nucleation efficiency. In this work, to study the influence of the orientation of nanoparticles on their performance in improving morphology of polymeric foam, thermoplastic polyurethane (TPU) composite fibers with different nanoparticles (carbon nanotubes, graphene and SiO₂) were prepared by using different traction speeds. The different traction speeds lead to different orientation state of the nanoparticles which then resulted different nucleation effect. It was found that carbon nanotubes (CNTs) were easily oriented and aligned along the fiber length direction under the high traction speed, while graphene and SiO₂ nanoparticles did not show orientation under the traction speed in this study. As a result, the foam of TPU/CNTs composite fibers from high traction speed exhibited a much smaller cell size and higher cell density compared to the foams of the fibers from low traction speeds, while TPU/graphene, and TPU/SiO₂ composite fibers with different traction speeds showed almost similar cell size and size density after foaming, indicating that the orientated nanoparticles possessed higher heterogeneous nucleation efficiency. To our best knowledge, this work, for the first time, demonstrated the high nucleation effect of the aligned nanoparticles, which hopefully open a new path for improving the cell morphology of polymeric foam materials.     

Effect of foaming temperature and rubber grades on properties of natural rubber foams

Foaming temperature and grade of dry natural rubber were varied to evaluate their effects on the morphology and mechanical properties of natural rubber (NR) foams. Three different grades of NR were used; namely ENR‐25, SMR‐L, and SMR‐10. NR foams from these grades were produced at three different foaming temperatures, i.e. 140, 150, and 160°C. The study was carried out using formulated compositions containing sodium bicarbonate as the chemical blowing agent and were expanded using conventional compression molding technique via a heat transfer foaming process. The NR foams were characterized with respect to their relative foam density, density of crosslinking, cell size, compression stress, and compression set. Increase in foaming temperature resulted in lower relative density and larger cell size. It was also discovered that the crosslink density slightly decrease with increasing foaming temperature. For mechanical properties, the highest foam density resulted in the highest compression stress. Compression stress at 50% strain increased with increasing foaming temperature and ENR‐25 foam has the highest compression stress among the produced foams. The results showed that the morphology, physical, and mechanical properties of the rubber foams can be controlled closely by the foaming temperature and rubber grades. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Foaming behavior of isotactic polypropylene in supercritical CO2 influenced by phase morphology via chain grafting

Polystyrene (PS) and poly(methyl methacrylate) (PMMA) grafted isotactic polypropylene copolymers (iPP-g-PS and iPP-g-PMMA) with well-defined chain structure were synthesized by atom transfer radical polymerization using a branched iPP (iPP-B) as polymerization precursor. The branched and grafted iPP were foamed by using supercritical CO₂ as the blowing agent with a batch method. Compared to linear iPP foam, the iPP-B foams had well-defined close cell structure and increased cell density resulted from increased melt strength. Further incorporating PS and PMMA graft chains into iPP-B decreased the crystal size and increased the crystal density of grafted copolymers. In iPP-g-PS foaming, the enhanced heterogeneous nucleation by crystalline/amorphous interface further decreased the cell size, increased the cell density, and uniformized the cell size distribution. In contrast to this, the iPP-g-PMMA foams exhibited the poor cell morphology, i.e., large amount of unfoamed regions and just a few cells distributed among those unfoamed regions, although the crystal size and crystal density of iPP-g-PMMA were similar to those of iPP-g-PS. It was found that the iPP-g-PMMA exhibited PMMA-rich dispersed phase, which had higher CO₂ solubility and lower nucleation energy barrier than copolymer matrix did. The preferential cell nucleation within the PMMA-rich phase or at its interface with the matrix accounted for the poor cell morphology. The different effect of phase morphology on the foaming behavior of PS and PMMA grafted copolymers is discussed with the classical nucleation theory.     

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.     

Structure and dielectric properties of polyimide/silica nanocomposite nanofoam prepared by solid‐state foaming

In this article, polyimide (PI)/silica nanocomposite nanofoams were prepared by solid‐state foaming using supercritical CO₂ as foaming agent. To control the cell size and morphology of the PI/silica foam, the silica nanoparticles as nucleating agent were in situ formation from TEOS via sol‐gel process, which make the silica nanoparticles homogeneously dispersed in PI matrix. The resulting PI/silica nanocomposite nanofoams were characterized by scanning electron microscopy (SEM), the image analysis system attached to the SEM and dielectric properties measurements. In PI/silica nanocomposite nanofoams, one type of novel morphology was shown that each cell contained one silica nanoparticle and many smaller holes about 20–50 nm uniformly located in the cell wall. This special structure could visually prove that the nucleation sites during foaming were formed on the surface of nucleating agents. Compared with those of neat PI foam, the cell size of PI/silica nanocomposite nanofoams was smaller and its distribution was narrower. The dielectric constant of PI/silica nanocomposite nanofoams was decreased because of the incorporation of the air voids into the PI/silica nanofoams. While the porosity of PI/silica nanocomposite nanofoam film was 0.45, the dielectric constant of the film (at 1 MHz) was reduced from 3.8 to about 2.6. Furthermore, the dielectric constant of PI/silica nanofoam films remained stable across the frequency range of 1×10²～1×10⁷ H_Z. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42355.     

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.     

Enhanced electrical conductivity in graphene-filled polycarbonate nanocomposites by microcellular foaming with sc-CO2

Electrically conductive polycarbonate (PC) foams containing a low concentration of graphene nanoplatelets (0.5 wt.%) were produced with variable range of expansion ratio by applying a high-pressure batch foaming process using sc-CO₂. The structure of the foams was assessed by means of SEM, AFM and WAXS, and the electrical conductivity was measured in the foam growing direction. Results showed that electrical conductivity of PC composite foams remarkably increased when compared to that of non-foamed PC composite, with both the electrical conductivity and the main cell size of the foams being directly affected by the resultant expansion ratio of the foam. This interesting result could be explained by the development of an interconnected graphene nanoparticle network composed by increasingly well-dispersed and reoriented graphene nanoplatelets, which was developed into the solid fraction of the foam upon foaming by sudden depressurising of the plasticised CO₂-saturated PC preform. Some evidences of morphological changes in the graphene nanoplatelets after foaming were obtained by analysing variations in graphene’s (0?0?2) diffraction plane, whose intensity decreased with foaming. A reduction of the average number of layers in the graphene nanoplatelets was also measured, both evidences indicating that improved dispersion of graphene nanoparticles existed in the PC composite foams. As a result, foams with a proper combination of low density and enhanced electrical conductivity could be produced, enabling them to be used in applications such as electromagnetic interference shielding.