HDPE/expanded graphite nanocomposites prepared via masterbatch process

High Density Polyethylene (HDPE) was melt extruded with different amounts of expanded graphite (EG) based masterbatches. Conductive composites were obtained by diluting PE and PS masterbatches with 60 wt% content of expanded graphite. These masterbatches were readily dispersed into the molten HDPE matrix yielding well‐dispersed HDPE/EG nanocomposites which couldn't be done by direct melt extrusion process under the same conditions. Electrical conductivity measurements showed a reduced percolation threshold by this masterbatch filling technique while the resulting composites were 2–3 orders of magnitude lower than that of direct melt extrusion because EG sheets were effectively encapsulated by PE or PS carriers in these masterbatches which leads to a better EG dispersion in composites. Both scanning electron microscopy (SEM) and X‐Ray diffraction (XRD) proved an excellent dispersion of EG in polymer matrix with the worm‐like structure tended to break into pieces under intensive rolling. The improvements in mechanical and thermal properties have been studied for the nanocomposites as prepared by masterbatch process. The results depended greatly on the dispersion of EG and the compatibility between masterbatch and HDPE matrix. POLYM. ENG. SCI., 47:882–888, 2007. © 2007 Society of Plastics Engineers     

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     

Synthesis and foaming of water expandable polystyrene-activated carbon (WEPSAC)

In this study, water acts as a co-blowing agent to support carbon dioxide (CO₂) in the extrusion foaming process of polystyrene (PS) to produce foams with very low density for thermal insulation applications. Herein, we report a simple suspension polymerization method to prepare water expandable polystyrene (WEPS) based on a PS/water containing activated carbon (AC) composite. AC pre-saturated with water was introduced into the styrene monomer to form a water-in-oil inverse emulsion without emulsifiers. Via suspension polymerization, water expandable PS/AC (WEPSAC) beads could be subsequently obtained. Low density PS foams (∼0.03 g/cc) were successfully produced in the CO₂ extrusion foaming process using WEPSAC. Because of lower foam density and better IR absorption due to the presence of water containing AC, WEPSAC foams provided a lower thermal conductivity than conventional talc reinforced PS foams.     

Characterization of conductive multiwall carbon nanotube/polystyrene composites prepared by latex technology

Conductive multiwall carbon nanotube/polystyrene (MWCNT/PS) composites are prepared based on latex technology. MWCNTs are first dispersed in aqueous solution of sodium dodecyl sulfate (SDS) driven by sonication and then mixed with different amounts of PS latex. From these mixtures MWCNT/PS composites were prepared by freeze-drying and compression molding. The dispersion of MWCNTs in aqueous SDS solution and in the PS matrix is monitored by UV–vis, transmission electron microscopy, electron tomography and scanning electron microscopy. When applying adequate preparation conditions, MWCNTs are well dispersed and homogeneously incorporated in the PS matrix. The percolation threshold for conduction is about 1.5 wt% of MWCNTs in the composites, and a maximum conductivity of about 1 S m⁻¹ can be achieved. The approach presented can be adapted to other MWCNT/polymer latex systems.     

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).     

Dispersion of nano-clay at higher levels into polypropylene with carbon dioxide in the presence of maleated polypropylene

The use of supercritical carbon dioxide (scCO₂) has proven to be beneficial for surface modified montmorillonite (MMT) nano-clay dispersion up to 6.6 wt% in a polypropylene (PP) matrix and lead to improved material mechanical properties in our earlier research. Our further modifications of the processing procedure including a sequential mixing technique successfully extended the technique to PP composites with as much as 10 wt% of clays and continuously increasing mechanical properties. In order to obtain additional enhancements of the composite properties at this clay level, polypropylene grafted with maleic anhydride (PP-g-MA) is included in this work. The results from the studies of the mechanical properties, rheological properties, and transmission electron microscopy (TEM) show that PP-g-MA is greatly beneficial in generating an exfoliated nano-clay morphology. Greater enhancements in the mechanical properties and nano-clay dispersion in the polymer matrix are observed when PP-g-MA is combined with the scCO₂ and sequential mixing techniques. The PP-g-MA based nano-clay composites have a high degree of exfoliated structure even with the addition of up to approximately 10 wt% nano-clay when using this technique, with mechanical properties such as yield strength and Young's modulus being increased by as much as 12 and 88%, respectively, relative to the polymer matrix. It is believed that the modulus reported here is the highest reported in the literature for conventional PP's.     

Effect of sodium oleate addition on the morphology of polypropylene-co-polyamide blends

The influence of sodium oleate additives on processing and morphology of polypropylene - co-polyamide (PP/CPA) mixture melts has been investigated. It is shown that sodium oleate is located in the interphase of the components and acts at small additives (up to 3 wt%) as an interfacial tension agent, improving miscibility of polymers, and increasing the kinetic stability of mixtures and the degree of PP dispersion in the co-polyamide matrix. The plasticizing effect on mixture melt was observed at 7 wt% sodium oleate as a reduction of mixture viscosity. The ultrathin PP fibers (microfibers) strictly oriented in the direction of extrusion are the main type of structure produced during extrusion of a PP/CPA mixture. Addition of sodium oleate changed the PP fiber-formation in the CPA matrix: the total number of fibers increased, their diameter and diameter distribution decreased.     

Influence of polymer matrix crystallinity on nanocomposite morphology and properties

In order to understand more fully how polymer matrix attributes influence polymer nanocomposite properties, nanocomposites containing hydroxyapatite nanoparticles and a poly(3-hydroxybutyrate) matrix were prepared and compared to results for a chemically-similar nanocomposite system with a lesser degree of matrix crystallinity. Experimental results indicated that the higher degree of matrix crystallinity hinders nanoparticle dispersion at loadings above 0.5 wt.% and together these structural factors, high matrix crystallinity and nanoparticle aggregation, produced different mechanical reinforcement behavior below and above the glass transition temperature than has been seen previously in amorphous matrices or matrices with moderate crystallinity levels. Overall, these results suggested that the amorphous character of the polymer does not govern the properties at all crystallinity levels in polymer nanocomposite matrices.     

Anisotropy in nanocellular polymers promoted by the addition of needle‐like sepiolites

This work presents a new strategy for obtaining nanocellular materials with high anisotropy ratios by means of the addition of needle‐like nanoparticles. Nanocellular polymers are of great interest due to their outstanding properties, whereas anisotropic structures allow the realization of improved thermal and mechanical properties in certain directions. Nanocomposites based on poly(methyl methacrylate) (PMMA) with nanometric sepiolites are generated by extrusion. From the extruded filaments, cellular materials are produced using a two‐step gas dissolution foaming method. The effect of adding various types and contents of sepiolites is investigated. As a result of the extrusion process, the needle‐like sepiolites are aligned in the machine direction in the solid nanocomposites. Regarding the cellular materials, the addition of sepiolites allows one to obtain anisotropic nanocellular polymers with cell sizes of 150 to 420 nm and cell nucleation densities of 10¹³–10¹⁴ nuclei cm^?3 and presenting anisotropy ratios ranging from 1.38 to 2.15, the extrusion direction being the direction of the anisotropy. To explain the appearance of anisotropy, a mechanism based on cell coalescence is proposed and discussed. In addition, it is shown that it is possible to control the anisotropy ratio of the PMMA/sepiolite nanocellular polymers by changing the amount of well‐dispersed sepiolites in the solid nanocomposites. © 2019 Society of Chemical Industry     

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     

Influence of twin-screw extrusion conditions on the dispersion of multi-walled carbon nanotubes in a poly(lactic acid) matrix

Twin-screw extrusion using a co-rotating Berstorff ZE25 extruder was applied to disperse multi-walled carbon nanotubes (MWNT) in poly(lactic acid) (PLA). The masterbatch dilution technique was used whereas four different masterbatches were produced under variation of MWNT content, screw profile, temperature profile, and rotation speed which then were diluted to composites with 0.75 wt% MWNT under varied process conditions. The state of dispersion was investigated by light microscopy from which a dispersion index was quantified. Transmission electron microscopy was performed to observe the MWNT dispersion and network formation in the sub-micron scale.The state of MWNT dispersion within the diluted composites was predominated by the state of filler dispersion in the masterbatches. High rotation speed (500 rpm) that still ensures a certain residence time of the melt combined with a screw profile containing mainly mixing elements were found to be highly convenient to disperse and distribute the MWNT in the PLA matrix as well during masterbatch production as the dilution step. The temperature profile showed less influence, however, an increasing profile resulted in slightly better nanotube dispersions. By means of these processing conditions a percolation set was performed indicating an electrical percolation threshold below 0.5 wt% MWNT content as measured on compression molded samples.     

Preparation of Polymer-Based Nanocomposites Composed of Sustainable Organo-Modified Needlelike Nanoparticles and Their Particle Dispersion States in the Matrix

Polymer-based nanohybrid materials were created using sustainable sepiolite clay composed from ubiquitous elements. Although sepiolite is generally recognized as a fibrous natural clay mineral, it turned out to be an acicular microcrystal because of the organo-modification of the outermost surface. Surface modification was performed using phosphonic acid derivatives containing hydrocarbon chains or fluorocarbon chains. Formation of a bidentate bond enhanced the desorption temperature and made nanocomposite preparation possible by melt compounding with polymers having a high melting point. As a result of organo-modification, amphiphilic sepiolite was obtained, and nanodispersion in an organic solvent was achieved. This technology was useful for detailed evaluation of sepiolite morphology. The nanocomposite of crystalline polymers/organo-modified sepiolites achieved uniform dispersion of these nanofillers in the matrix polymer. The introduction of 1 wt% nanofillers did not impair the transparency of the matrix polymer. As a result, a lamellae structure of the polymer developed, the crystallinity increased, and the mechanical properties improved. In addition, the crystallization temperature was improved, indicating that organo-modified sepiolites may act as a nucleating agent. It was found that sepiolite nanofiller with a highly aggregated tendency can achieve a well-nanodispersed state, even in phase-separable fluoropolymers, by applying fluorocarbon modification. POLYM. ENG. SCI., 60:541–552, 2020. © 2019 Society of Plastics Engineers     

Extruded PLA/clay nanocomposite foams blown with supercritical CO2

The effects of nanoclay (Cloisite 30B) on the foamability of polylactide (PLA) were investigated in continuous extrusion foaming using supercritical CO₂ as the blowing agent. PLA samples containing 0–5 wt% of nanoclay were prepared. The X-ray diffraction and transmission electron microscopy images showed a high degree of exfoliation of clay nanoparticles within PLA. A single-screw tandem extruder was used to produce foams with 5 wt% and 9 wt% supercritical CO₂. The crystallization behavior of the samples was analyzed using regular and high-pressure differential scanning calorimeters and using a rotational rheometer under small amplitude oscillatory shearing. In the presence of dissolved CO₂, clay, and shear action, the PLA crystallization kinetics was significantly enhanced. The foamed results showed that both the cell density and the expansion ratio were greatly promoted with increased clay content and the dissolved CO₂, as well as by the possibly nucleated crystals. By further use of Cloisite 20A nanoclay particles with poor disperse-ability in PLA, we also proved that a high degree of dispersion significantly promoted the cell density and the expansion ratio of the PLA nanocomposites. Further, by varying the temperature profile within second extruder of the tandem-line, it was confirmed that the more rapid crystallization along the second extruder was responsible for the enhanced cell density and expansion ratio. The final crystallinity of the foamed samples was also enhanced at higher expansion ratios due to the strain induced crystallization.     

An efficient interface model to develop scalable methodology of melt processing of polypropylene with graphene oxide produced by an improved and eco-friendly electrochemical exfoliation

This study developed a scalable and straightforward adaptation methodology for melt processing of polypropylene (PP) to provide a high degree of exfoliation of multilayer graphene oxide (GO) by using a high-shear mixer. GO was first produced by an improved and eco-friendly electrochemical exfoliation by using an environmentally friendly aqueous methanesulfonic acid (MSA) and a sodium sulfate salt system to minimize the environmental impact. The produced GOs then were melt blended with PP and their mechanical, thermal, and morphological properties were investigated under different GO loadings to attain ideal configuration and increase interfacial interactions between polymer matrix and reinforcer. Comparisons were made by producing different PP composites using two different GO types produced in salt and acid environments. Additionally, by applying different voltages to salt system, the effect of applied voltage on the properties of both GO material and the composites were discussed. The characterization results indicated that GO obtained in MSA solution caused a 71% increase in flexural modulus and 46% in flexural strength with the addition of 1 wt% GO. The rheological characterization also showed that dispersion and viscosity improved with lower GO loadings compared to neat polymer by providing cost-effective and scalable graphene manufacturing.     

Analysis of the foaming mechanisms of materials based on high‐density polyethylene (HDPE) crosslinked with different irradiation doses

Different crosslinked high‐density polyethylene based cellular polymers have been produced by a free foaming process using a chemical blowing agent. The polymer matrix was crosslinked by electron beam irradiation using different doses ranging from 25 to 175 kGy. The main aim of this work is to study the effect of the different irradiation doses on the density, cellular structure, and foaming mechanisms. Results show that irradiation doses as high as 175 kGy have to be used to obtain cellular materials with a low relative density (0.06), cell sizes of around 50 μm, and cell densities of 1.6 × 10⁷ cells cm^?3. The strain hardening of the polymer matrix increases with the irradiation dose leading to an increase of the polymer resistance to be stretched, which helps to avoid undesirable cellular degeneration processes. Irradiation doses lower than 175 kGy are not able to stabilize the cellular structure leading to foams with relative densities higher than 0.1 and degenerated cellular structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46276.     

Asphaltene/polymer composites: Morphology,compatibility, and rheological properties

In this study, we investigate the use of asphaltene, a natural waste product that is inevitably formed during heavy oil processing, as a filler in polymer composites. The focus of this work is on the compatibility of various asphaltenes, featuring different polarities, with several polymers, including polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA), and polycarbonate (PC). The Hansen solubility parameters were plotted to predict the compatibility of polymers with different asphaltenes. Then, polymer composites were prepared by two common techniques: melt mixing and solution mixing. The dispersion state of the asphaltenes in each polymer was investigated by using imaging and rheological techniques. This work showed that the network structure of the asphaltenes and, thus, the final properties of the composites can be controlled by the polarity of asphaltenes, mixing technique, and melt viscosity of the polymer. For instance, more polar asphaltene (Asph P) produced smaller aggregates in PMMA, which has a higher polar solubility parameter than PP or PS. At 2.5 wt.% of asphaltene, Asph P showed 26% and 177% larger asphaltene agglomerates in PP and PS, respectively, than the less polar asphaltene (Asph Al). PS/asphaltene and PMMA/asphaltene composites prepared by the solution mixing method exhibited better dispersion compared to their melt-mixed counterparts. In melt-mixed composites, the dispersion quality of the asphaltene was better for polymers with higher melt viscosity. Thus, a careful choice of polymer, asphaltene, and preparation conditions can be used to tune the properties of asphaltene/polymer composites.     

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.     

Effect of organoclay on the morphology, phase stability and mechanical properties of polypropylene/polystyrene blends

The effect of organically modified clay on the morphology, phase stability and mechanical properties of polypropylene (PP) and polystyrene (PS) blends was studied using three molecular weight grades of PP. Maleated polypropylene was used, at a PP-g-MA/organoclay ratio of 1, to preferentially promote dispersion of the organoclay in the PP matrix. The MMT content was fixed at 3 wt% based on the PP/PP-g-MA/MMT phase and the PS content was varied from 0-100 wt% in the blend. All blends were processed using a twin screw extruder. The organoclay resides in the PP phase and at the PP/PS interface. The dispersed PS particle size is significantly reduced by the presence of MMT, with maximum decrease observed for the low viscosity PP compared to its blend without MMT. The blends with MMT did not show any change in onset of co-continuity, though MMT shifts the phase inversion composition toward lower PS contents. The phase stability of the blend was significantly improved by the presence of MMT; for blends annealed at 210 °C for 2 h the dispersed phase particle size increased by as much as 10x without MMT with little change was noted with MMT present in the blend. The tensile modulus of blends improved with the addition of MMT at low PS contents. Blends based on the highest molecular weight grade PP showed increase in the tensile yield stress up to 40 wt% PS in the absence of MMT. The tensile strength at break for blend increased slightly with MMT while elongation at break and impact strength decreased in the presence of MMT. Surface energy analysis model was used to predict the orientation and equilibrium position of the clay platelet at the interface based on the surface energies.     

Novel design of alumina foams with three-dimensional reticular architecture for effective high-temperature particulate matter capture

Ceramic foams with extensive interconnected pores have great application potential in high-temperature particulate matter (PM) capture. Considering that there are still challenges to synthesize ceramic foams with efficient filtration, a novel hierarchical-structured alumina foam with three-dimensional (3D) reticular architecture has been fabricated via combining chemical grafting pore-forming agent and polyurethane (PU) foaming technology. Carbon black is grafted with carbamate functional groups in order to enable a better dispersion in highly viscous PU. Submicrometer and micrometer-sized pores on the cell walls are observed in hierarchical-structured ceramic foams. The resulting alumina foam exhibits 95.2% removal efficiency for PM particles and low pressure drop of only 50 Pa when grafted carbon black content is 3 wt%. This filtration performance is much higher than that of existing ceramic materials. These features, combined with our experimental design strategy, provide a new insight to design high-temperature PM filtration materials with durable high performance.     

Effect of organically modified montmorillonite (OMMT) on biodegradation of PS:PLA and PS:PLA:OMMT using Phanerochaete chrysosporium

The environmental issues of synthetic polymers have been resolved using biodegradation under controlled conditions. The degradation study of polymeric composites of (a) polystyrene (PS) and poly(lactic acid) (PLA) (PS:PLA), and (b) PS:PLA filled with organically modified montmorillonite (OMMT) (PS:PLA:OMMT) was carried out using Phanerochaete chrysosporium . PLA was synthesized using l ‐lactic acid under controlled ultrasound cavitation technique, dried and added to a solution of PS. Surface of montmorillonite (MMT) was modified using column chromatographic technique to improve d‐spacing up to 31.5 Å. The sheets of PS:PLA and PS:PLA:OMMT were subjected to degradation study in minimal medium using P. chrysosporium micro‐organism under controlled conditions up to 28 days. The growth of micro‐organism and fractures inside the polymer matrix before and after degradation was observed using scanning electron microscope. Change in extracellular protein content, biomass production, and % degradation with respect to time of incubated samples have been also studied. It was found that the PS:PLA:OMMT (at 5 phr OMMT content) and PS:PLA (at 30% PLA) composites show an increment in degradation. The presence of OMMT leads to faster degradation of PS:PLA:OMMT nanocomposites, which decreases in mechanical property by 30% of PLA and 5 wt% of OMMT content. POLYM. COMPOS., 38:1292–1301, 2017. © 2015 Society of Plastics Engineers