Microcellular foams of glass–fiber reinforced poly(phenylene sulfide) composites generated using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide) (PPS) and its glass–fiber (GF) reinforced composites using supercritical CO₂ as a blowing agent presents a promising approach to produce novel cellular materials with tailored microstructures. This study investigated the effects of the material composition and process conditions on the foaming behaviors and final morphologies of the microcellular foamed PPS and PPS/GF composites. The rheological and thermal properties as well as the saturation and desorption behaviors of CO₂ in the pure PPS and PPS/GF composites were also detailedly discussed. The results show that microcellular foams with various relative densities, cell sizes, cell‐size distributions, and cell densities can be attained by tailoring the fiber content and key process parameters. At low foaming temperatures below the cold crystallization temperature, the microcellular foamed PPS and PPS/GF composites both present a unimodal cell‐size distribution. At elevated temperatures, the generated crystalline superstructures including spherulites in the polymer matrix and transcrystals around the GF will cause a secondary heterogeneous cell nucleation. This leads to the observations of bimodal and trimodal cell‐size distributions in the pure PPS and the PPS/GF composites, respectively. The mechanisms for the solid‐state foaming behaviors of pure PPS and PPS/GF composites have been illustrated by establishing theoretical models. POLYM. COMPOS., 37:2527–2540, 2016. © 2015 Society of Plastics Engineers     

Open‐celled microcellular thermoplastic foam

A theoritical model of the production of open‐cell microcellular foam is presented. This model allows the prediction of the conditions necessary to produce these materials. Experiments verify the model quite well. The results of the batch processing experiments indicate the processing parameters that promote the development of open‐celled microcellular polystryene foam. A saturation pressure of 17.2 MPa (2500 psig) provides the nucleation density necessary to form an impinged structure with microcellular bubble density. A foaming temperature of 200°C promotes the formation of both internal and surface porosity. A scaled time between 1 and 2.7 seconds develops a foam structure that intrudes a large volume. Samples foamed at 200°C for 1 and 2 seconds possess pores less than 1 μm in diameter. These samples represent scaled times of 1 and 2 seconds. Therefore, to produce open‐celled microcellular polystyrene foam with batch processing, samples should be saturated at approximately 17.2 MPa (2500 psig) and foamed for a scaled time between 1 and 2 seconds.     

Investigation of a strategy for well controlled inducement of microcellular and nanocellular morphologies in polymers

This study is an effort to modify conventional batch processes to be able to produce polymeric foams with high cell density and small cell size, which cannot be reached by conventional batch foaming processes. This has been attained by controlling the foaming temperature and controlled stabilization of the cellular structure. The method was tested for both with and without addition of nanosized particles in polymeric matrix. The desired morphologies were obtained using a novel apparatus with the capability of instantaneous pressure drop and controlling stabilization of the foam structure. The design of the said apparatus was based on the idea that in a foaming process, nucleation is the predominant mechanism that determines the final foam structure. The produced foam products have uniform structures without any unfoamed skin. Results show that the control of the foaming temperature and the cell stabilization are the predominant factors in adjustment of the final foam morphology. A wide range of microcellular structures with cell densities between 10⁷ and 10¹² bubbles/cm³ and average cell sizes of 500 nm–20 μm were produced. Foaming of polystyrene‐nano‐silica nano‐composites with the same method showed that nanoparticles act as nucleating agent and increase the cell density in the final foam products compared with that of neat polystyrene. POLYM. ENG. SCI., 50:1558–1570, 2010. © 2010 Society of Plastics Engineers     

Ultrasound‐induced nucleation in microcellular polymers

In this study, microcellular Acrylonitrile–Butadiene–Styrene foams with high cell density and expansion ratio has been manufactured using ultrasound‐induced nucleation technique in solid‐state batch foaming process. Influence of sonication time, sonication frequency, and ultrasound power were found very crucial in designing of cellular morphology. The initial 10 s of ultrasound exposure was found to influence the foam morphology critically. Longer periods of ultrasound exposure developed foams with lower average cell size as compared to foams developed with lesser ultrasound exposure time. Higher sonication power resulted in foams with uniform morphology and higher cell densities as compared to foams developed with lower sonication intensities. Finally, the ultrasonic frequency was also found to influence the morphology intensely. Low frequency sonication resulted in foams with uniform cell distribution, whereas high frequency sonication developed bimodal microcellular type of microstructure. The results coherently demonstrate that with the advent of ultrasonic waves, the energy barrier for cell nucleation swiftly decreases which enhances the cell density in the final foamed product. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40742.     

Low density microcellular foam processing in extrusion using CO2

A continuous extrusion process for the manufacture of low-density microcellular polymers is presented. Microcellular polymers are foamed plastics characterized by a cell density greater than 10⁹ cells/cm³ and a fully grown cell size on the order of 10 μm. Previous research on continuous processing of microcellular polymers has focused on control of microcell nucleation in extrusion. This paper presents an effective means for control of cell growth to achieve a desired expansion ratio with CO₂ as a blowing agent in microcellular foam processing. Also, a strategy to prevent deterioration of the cell-population density via cell coalescence during expansion is presented. Promotion of a desired volume expansion ratio and prevention of cell coalescence in microcellular foam processing were experimentally verified. By tailoring the extrusion processing parameters, microcellular HIPS foams with a cell density of 10¹⁰ cells/cm³ and a controlled expansion ratio in the range of 1.5 to 23 were obtained.     

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.     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

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.     

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     

Effect of processing parameters on cell morphology of polycarbonate foam

Abstract

The purpose of this research is to investigate the effect of processing parameters on the cell morphology of polycarbonate (PC) foam. In this study, foamed PC was prepared using a dynamic simulation foaming set-up. The cell morphology was compared at different temperatures, pressures, gas saturation times, pressure drop rates and shear rates. The cell morphology of foamed samples was characterised using SEM. It was found that foamed samples with better morphology could be obtained by varying mechanical properties, such as pressure, pressure drop rate and gas saturation time. Optimum temperature and shear rate for microcellular foaming of PC are presented.     

Effect of the crystallinity and morphology on the microcellular foam structure of semicrystalline polymers

Microcellular foam processing of polymers requires a nucleated cell density greater than 10⁹ cells/cm³ so that the fully grown cells are smaller than 10 μm. A microcellular foam can be developed by first saturating a polymer sample with a volatile blowing agent, followed by rapidly decreasing its solubility in the polymer. In general, the cellular structure of semicrystalline polymer foams is difficult to control, compared to that of amorphous polymer foams. Since the gas does not dissolve in the crystallites (1), the polymer/gas solution formed during the microcellular processing is nonuniform. Moreover, the bubble nucleation is nonhomogeneous because of the heterogeneous nature of the semicrystalline polymer. In this paper, the effects of the crystallinity and morphology of semicrystalline polymers on the microcellular foam processing and on the cellular structure of products are investigated. First, polymer specimens with various crystallinities and morphologies were prepared by varying the cooling rate of the polymer melt. Then, the solubility and diffusivity of the blowing agent in and through specimens were studied. The specimens with differing crystallinities and morphologies were foamed and their cellular structures were compared. The experimental results agree with theoretical predictions, indicating that the crystallinity and morphology of semicrystalline polymers exert a strong influence on the foam processing and the structure of the product.     

Investigation on the cell nucleation and cell growth in microcellular foaming by means of temperature quenching

The cell nucleation and real‐time cell growth with increasing cell growth time in microcellular foaming were investigated by means of temperature quenching in a supercritical CO₂ pressure‐quench process. Samples of uniform size and shape were saturated in a vessel under conditions of 100–180°C and 30 MPa, and then depressurized to the atmosphere in 10 s. After depressurization, these samples were removed from the vessel at prescribed intervals, and immediately immersed in an ice‐water slurry to obtain foamed samples with various cell growth times. It was found that the nucleation density is closely correlated to the gas absorption capacity of the polymer matrix, so that the final cell density should not be adopted as the nucleation density, as done commonly. The change of cell structure and mass density with increasing cell growth time was dominated by gas diffusion behavior, which was strongly influenced by the temperature. The final cell structure was mainly determined by the cell growth step, where gas diffusion played a key role. The final cell density was in direct proportion to the gas remaining in the substrate, which ranged from 6.0 × 10⁹ to 4.7 × 10⁶ cells/cm³. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 163–171, 2004     

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

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

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.     

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.     

振动力场对含有成核剂的微孔塑料泡孔结构的影响

在微孔塑料成型加工过程中,成核剂的加入可以增加泡孔成核点数量,从而增加泡孔密度,改善泡孔的结构,但如果纳米级成核剂在发泡过程中分散性不好,会使泡孔分布不均匀,影响泡孔质量。在实验中,对含有成核剂(纳米碳酸钙)的发泡材料(聚苯乙烯)施加振动场,通过比较发现,施加振动后,纳米级成核剂的分散效果明显改善,颗粒分布变得更均匀,从而使得泡孔分布更均匀,改善了泡孔的结构,提高了微孔塑料泡孔结构质量。     

Generation of microcellular polymeric foams using supercritical carbon dioxide. II: Cell growth and skin formation

We have generated microcellular polymeric foam structures using a pressure induced phase separation in concentrated mixtures of supercritical CO₂ and poly(methyl methacrylate). The process typically generates a microcellular core structure encased by a nonporous skin, the thickness of which decreases with increasing saturation pressure. This trend can be described by a model for skin formation that is based on the diffusion rate of gas out of the sample. Significant density reductions on the order of 30 to 70% can be achieved by changing the pressure and temperature conditions in the foaming process. There are several ways in which the saturation pressure affects the average cell size, with the net effect that cell size decreases sharply with increasing pressure above 2000 psi, leveling out at higher pressures. Cell size increases with increasing temperature from 40°C to 70°C. A model for cell growth, based on a cell model of Aremanesh and Advani, modified to include the effect of CO₂ on model parameters, reproduces these trends.     

微孔发泡注塑技术研究进展

介绍了微孔发泡塑料的定义及优点,阐述并对比了物理微孔发泡和化学微孔发泡等2种微孔发泡注塑成型工艺;详细介绍了近年来微孔发泡注塑技术在工艺优化、开模二次发泡、表面质量改善和力学性能预估等方面的最新研究进展;最后,对微孔发泡注塑技术未来的研究方向进行了展望。     

Cell morphology and property relationships of microcellular foamed pvc/wood-fiber composites

Wood-fiber composites make use of cellulose fibers as a reinforcing filler in the polymer matrix and are known to have a lower material cost and a higher stiffness than neat polymers. However, the lower material cost and enhanced stiffness of wood-fiber composites are achieved at the expense of other properties such as the ductility and impact strength. Since microcellular plastics exhibit a higher impact strength, higher toughness, and increased fatigue life compared to unfoamed plastics, microcellular foaming of wood-fiber composites will improve the mechanical properties of the composites and therefore increase the usefulness of the materials. In this paper, microcellular foamed PVC/wood-fiber composites with unique cell morphology and material composition are characterized. Microcellular structures are produced in PVC/wood-fiber composites by first saturating the composite samples with CO₂ under high pressure followed by rapidly decreasing the solubility of gas in the samples. The void fraction of the microcellular foamed PVC/wood-fiber composites is controlled by tailoring the composition of materials and the foaming process parameters. The results indicate that tensile and impact properties of microcellular foamed PVC/wood-fiber composites are most sensitive to changes in the cell morphology and the surface modification of fibers.     

N2‐filled hollow glass beads as novel gas carriers for microcellular polyethylene

N₂‐filled hollow glass beads (HGB) were first used as novel gas carriers to prepare microcellular polymers by compression molding. Dicumyl peroxide was acted as crosslink agent to control the produced microcellular structure of low density polyethylene (LDPE)/HGB. The effect of temperature, pressure and the content of gel on the embryo‐foaming, and final‐foaming structure are investigated. Scanning electronic microscopy shows that the average cell size of microcellular LDPE ranges from 0.1 to 10 μm, and the foam density is about 10⁹–10¹¹ cells/cm³. A clear correlation is established between preserving desirable micromorphologies of microcellular LDPE in different processing stage and tuning processing factors. The pertinent foaming mechanism of microcellular materials foamed with HGB is proposed. Because of the good mechanical strength, low density, weak water‐absorption, and excellent heat insulate ability, microcellular LDPE has great potential application in energy building materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009