Co-continuous Morphology Research Articles

Evolution of morphology and electrical properties under controlled flow in polypropylene/polystyrene co-continuous blends containing interfacially localized carbonaceous nanoparticles

This study investigates the evolution of morphology and electrical properties of polypropylene (PP)/polystyrene (PS) blend nanocomposites under controlled steady shear flow. These nanocomposites contain either few-layer graphene (FLG) or a mixture of FLG and multi-walled carbon nanotubes (MWCNT), prepared via a conventional melt-mixing. Composites were created by premixing FLG or FLG/MWCNT with either PP [PP/PS/FLG or PP/PS/(FLG+MWCNT)] or PS [PS/PP/FLG or PS/PP/(FLG+MWCNT)] at a PP/PS ratio inducing co-continuous morphology. Results showed a significant reduction in the percolation threshold (PT) for PS/PP/FLG composites, with an 81% decrease compared to PS/FLG. When FLG was premixed with PS, PT required only 2 wt. % FLG, compared to 5.9 wt. % in PP/PS/FLG. Steady shear deformation disrupted the electrical network in both PP/PS/FLG and PS/PP/FLG composites. However, the PS/PP/FLG composites exhibited greater stability in electrical conductivity at lower FLG concentrations (above 3 wt. %) compared to the PP/PS/FLG composites (above 6 wt. %). The applied shear did not affect the co-continuous morphology of the blend-based composites containing 1 wt. % or more of FLG. Additionally, the synergistic effects of the hybrid FLG/MWCNT mixture on the electrical conductivity and rheological properties of both PP/PS/(FLG+MWCNT) and PS/PP/(FLG+MWCNT) composites were evaluated. The incorporation of MWCNT into both PP/PS/FLG and PS/PP/FLG composites significantly enhanced the formation of a hybrid electrical network structure, leading to a further reduction in the percolation threshold concentration of FLG. Specifically, in PP/PS/FLG composites, PT decreased from 5.9 to 1–3 wt. % of FLG, while in PS/PP/FLG composites, PT dropped from 2 to 1 wt. % of FLG.

Toughening Immiscible Polymer Blends: The Role of Interface-Crystallization-Induced Compatibilization Explored Through Nanoscale Visualization.

This study explores the novel approach of interface-crystallization-induced compatibilization (ICIC) via stereocomplexation as a promising method to improve the interfacial strength in thermodynamically immiscible polymers. Herein, two distinct reactive interfacial compatibilizers, poly(styrene-co-glycidyl methacrylate)-graft-poly(l-lactic acid) (SAL) and poly(styrene-co-glycidyl methacrylate)-graft-poly(d-lactic acid) (SAD) are synthesized via reactive melt blending in an integrated grafting and blending process. This approach is demonstrated to enhance the interfacial strength of immiscible polyvinylidene fluoride/poly l-lactic acid (PVDF/PLLA) 50/50 blends via ICIC. IR nanoimaging indicates a cocontinuous morphology in the blends. The blend compatibilized with SAD exhibits a higher storage modulus, as unveiled by small amplitude oscillatory shear (SAOS) in the melt state at a temperature below the melting temperature of the stereocomplex (SC) crystals and by DMTA measurements in the solid state. This increase is attributed to the formation of a 200-300 nm thick rigid interfacial SC crystalline layer that is directly visible using AFM imaging and chemically characterized via IR nanospectroscopy. This ICIC also results in a significant toughening of the blend, with the elongation at break increasing more than 20-fold. Moreover, the fracture toughness factor obtained from single edge-notch bending (SENB) tests is doubled with ICIC as compared to the uncompatibilized blend, indicating the strong crack-resistance capability as a result of ICIC. This improvement is also evident in SEM images, where thinner and longer fibrillation is observed on the fractured surface in the presence of ICIC.

BioMOF@PAN Mixed Matrix Membranes as Fast and Efficient Adsorbing Materials for Multiple Heavy Metals' Removal.

Heavy metal ions are a common source of water pollution. In this study, two novel membranes with biobased metal-organic frameworks (BioMOFs) embedded in a polyacrylonitrile matrix with tailored porosity were prepared via nonsolvent induced phase separation methods and designed to efficiently adsorb heavy metal ions from oligomineral water. Under optimized preparation conditions, stable membranes with high MOF loading up to 50 wt % and a cocontinuous sponge-like morphology and a high water permeability of 50-60 L m-2 h-1 bar-1 were obtained. The tortuous flow path in combination with a low water flow rate guarantees maximum contact time between the fluid and the MOFs, and thus a high heavy metal capture efficiency in a single pass. The performances of these BioMOF@PAN membranes were investigated in the dynamic regime for the simultaneous removal of Pb2+, Cd2+, and Hg2+ heavy metals from aqueous environments in the presence of common interfering ions. The new composite adsorbing membranes are capable of reducing the concentration of heavy metal pollutants in a single pass and at much higher efficiency than previously reported membranes. The enhanced performance of the mixed matrix membranes is attributed to the presence of multiple recognition sites which densely decorate the BioMOF channels: (i) the thioether groups, deriving from the S-methyl-l-cysteine and (S)-methionine amino acid residues, able to recognize and capture Pb2+ and Hg2+ ions and (ii) the oxygen atoms of the oxamate moieties, which preferentially interact with Cd2+ ions, as revealed by single crystal X-ray diffraction. The flexibility of the pore environments allows these sites to work synergically for the simultaneous capture of different metal ions. The stability of the membranes for a potential regeneration process, a key-factor for the effective feasibility of the process in real life applications, was also evaluated and confirmed less than 1% capacity loss in each cycle.

The Effect of Zn2(BDC)2 Metal Organic Framework on the Miscibility and Properties of Poly(Lactic Acid)/Poly(Butylene Adipate-co-Terephthalate) Biodegradable Blends

In our research described in this paper, the metal-organic framework MOF-2 [Zn2(BDC)2] was used to enhance the properties of a biodegradable blend based on poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT). PLA/PBAT/(1, 3, 5, and 7 wt%) MOF-2 blends were prepared using a melt blending technology with a twin-screw extruder. The phase morphology, rheological behavior and barrier properties of the blends were studied. X-ray diffraction (XRD) showed a slight increase in the crystalline content of the PLA/PBAT matrix with increasing MOF-2 content. Scanning electron microscopy (SEM) revealed that the PLA/PBAT blend was immiscible, and the phase morphology improved with MOF-2 by enhancing the interfacial compatibility, reducing the size of micro-domains and cavities, and promoting a transition to a co-continuous morphology, indicating better miscibility. The ternary nanocomposites with 5 and 7 wt% MOF-2 showed increased complex viscosity (η*) and storage modulus (G′) compared to those with 1 and 3% MOF-2, indicating stronger percolated networks. The thermal and barrier properties and water absorption capacity were also improved, confirming the rheological measurements. All the results showed that the PLA/PBAT/MOF-2 nanocomposites could be used in the field of packaging.

Fabrication of co-continuous morphology of polysulfone/nylon 6, 6 nanocomposites by varying the concentration of organically modified clay content

A unique morphology was fabricated using melt mixing of polysulfone (PSU) and nylon 6, 6, as well as organically modified clay to produce two blended nanocomposite compositions (80/20 and 60/40 w/w) of polysulfone and nylon 6, 6. The morphology of PSU/Nylon 6, 6 blend nanocomposites with various amounts of clay has been examined using scanning electron microscope (SEM), transmission electron microscope (TEM), and wide-angle X-ray diffraction (WAXD). In the case of 80/20 (w/w) PSU/Nylon 6, 6 without clay, the Nylon 6, 6 is dispersed in the PSU matrix with an average particle size of about 6.81 micrometers (μm). After adding clay (2%, 4%, and 8%), the domain size of nylon 6, 6 decreases, although the decrease rate is much slower than initially observed. However, we discovered that when the organoclay level exceeds 2%, the matrix-domain structure transforms into a co-continuous morphology for the 60/40 (w/w) blends. The TEM studies clearly demonstrate that the organoclay preferentially positions itself in the nylon 6, 6 phase, exhibiting a high degree of exfoliation, while the PSU phase of the nanocomposites remains devoid of clay, irrespective of the amount present. This study indicates that the size of clay platelets dispersed in the PSU/Nylon 6, 6 blend plays an important role in determining the morphology and stability of these blends. Moreover, the co-continuous structures were stable against further annealing at high temperatures, thus inhibiting the coalescence of the dispersed phase in addition to reducing interfacial tension.

Processing and Evaluation of Bio-Based Paramylon Ester/Poly(butylene succinate) Blends for Industrial Applications

Poly(butylene succinate) (PBS) was melt-blended with paramylon based mixed ester, paramylon propionate hexanoate (PaPrHe) and characterized for its morphology, thermal and mechanical properties. The PBS/PaPrHe blends were found to be immiscible throughout the loading range of PaPrHe (10–90 wt%), with individual glass transition peaks. Due to the immiscibility, there was phase separation observed in the bulk, evident by sea-island morphology. However, further observation of the micro-structure revealed that, in low PaPrHe loading (10–30 wt%), there was a micron to sub-micron order distribution of PBS particles and partially miscible PBS/PaPrHe phase. On increasing the PaPrHe to 50 wt% and beyond, the sub-micron scale domains fused to form a co-continuous morphology. As a result, the impact strength of PBS increased from 6.6 to 16.4 kJ/m2 in the 50/50 blend. Under tensile loading, the strength at break and elongation decreased after the introduction of less-flexible PaPrHe particles in the blend. This could be countered by uniaxially stretching the blended films with 10–30 wt% PaPrHe, after which the tensile strength increased by up to 380% (from 33–52 MPa to 165–200 MPa) compared to the unstretched films, attributable to the increased degree of orientation of the molecular chains. In terms of thermal processability, all the blend ratios had high thermal degradation temperature (>350 °C), higher than the melt-flow temperature (124–133 °C) providing a wide processing window. Overall, PBS/PaPrHe blend is a novel bio-based blend with properties suitable for packaging, mulching, and related applications.

Facile Synthesis of Poly(methyl methacrylate) Silica Nanocomposite Monolith by In Situ Free Radical Polymerization of Methyl Methacrylate in the Presence of Functionalized Silica Nanoparticles.

Novel porous poly(methyl methacrylate) (PMMA) silica nanocomposites have been produced by utilization of polymerization-induced phase separation in a simple one-pot approach. A facile free radical polymerization of MMA in the presence of surface methacrylate-functionalized silica nanoparticles was carried out in ethanol-based solvents, successfully producing novel, morphologically designable porous nanocomposite monoliths. Differing from standard free radical polymerization in solution, a mixture of good and poor solvents (ethanol/N,N-dimethylformamide ratio) for the resulting polymer was used to trigger spinodal phase separation. The influence of monomer concentration, as well as solvent composition, on the morphology of the resulting porous polymers has been investigated. Porous monolith structures composed of connected particles and co-continuous morphologies were observed under a scanning electron microscope depending on the polymerization conditions. The resulting polymers were insoluble and showed swelling characteristics in some organic solvents that are capable of dissolving regular PMMA, indicating covalent bonds between the functionalized silica nanoparticles and the polymer chains. The presence of silica particles in the final polymer was proven via an ATR-IR analysis. The glass transition temperature of the present PMMA-silica nanocomposite was higher than that of the conventional PMMA. The porous polymer immersed in a mixed organic solvent showed coloration induced by the Christiansen effect.

Phase Morphology and Mechanical Properties of Super-Tough PLLA/TPE/EMA-GMA Ternary Blends.

The inherent brittleness of poly(lactic acid) (PLA) limits its use in a wider range of applications that require plastic deformation at higher stress levels. To overcome this, a series of poly(l-lactic acid) (PLLA)/biodegradable thermoplastic polyester elastomer (TPE) blends and their ternary blends with an ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) copolymer as a compatibilizer were prepared via melt blending to improve the poor impact strength and low ductility of PLAs. The thermal behavior, crystallinity, and miscibility of the binary and ternary blends were analyzed by differential scanning calorimetry (DSC). Tensile tests revealed a brittle-ductile transition when the binary PLLA/20TPE blend was compatibilized by 8.6 wt. % EMA-GMA, and the elongation at break increased from 10.9% to 227%. The "super tough" behavior of the PLLA/30TPE/12.9EMA-GMA ternary blend with the incomplete break and notched impact strength of 89.2 kJ∙m-2 was observed at an ambient temperature (23 °C). In addition, unnotched PLLA/40TPE samples showed a tremendous improvement in crack initiation resistance at sub-zero test conditions (-40 °C) with an impact strength of 178.1 kJ∙m-2. Morphological observation by scanning electron microscopy (SEM) indicates that EMA-GMA is preferentially located at the PLLA/TPE interphase, where it is partially incorporated into the matrix and partially encapsulates the TPE. The excellent combination of good interfacial adhesion, debonding cavitation, and subsequent matrix shear yielding worked synergistically with the phase transition from sea-island to co-continuous morphology to form an interesting super-toughening mechanism.

Block copolymer self-assembly derived mesoporous magnetic materials with three-dimensionally (3D) co-continuous gyroid nanostructure.

Magnetic nanomaterials are gaining interest for their many applications in technological areas from information science and computing to next-generation quantum energy materials. While magnetic materials have historically been nanostructured through techniques such as lithography and molecular beam epitaxy, there has recently been growing interest in using soft matter self-assembly. In this work, a triblock terpolymer, poly(isoprene-block-styrene-block-ethylene oxide) (ISO), is used as a structure directing agent for aluminosilicate sol nanoparticles and magnetic material precursors to generate organic-inorganic bulk hybrid films with co-continuous morphology. After thermal processing into mesoporous materials, results from a combination of small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are consistent with the double gyroid morphology. Nitrogen sorption measurements reveal a type IV isotherm with H1 hysteresis, and yield a specific surface area of around 200 m2 g-1 and an average pore size of 23 nm. The magnetization of the mesostructured material as a function of applied field shows magnetic hysteresis and coercivity at 300 K and 10 K. Comparison of magnetic measurements between the mesoporous gyroid and an unstructured bulk magnetic material, derived from the identical inorganic precursors, reveals the structured material exhibits a coercivity of 250 Oe, opposed to 148 Oe for the unstructured at 10 K, and presence of remnant magnetic moment not conventionally found in bulk hematite; both of these properties are attributed to the mesostructure. This scalable route to mesoporous magnetic materials with co-continuous morphologies from block copolymer self-assembly may provide a pathway to advanced magnetic nanomaterials with a range of potential applications.

“Interface localization of reduced graphene oxide in polystyrene/polymethyl methacrylate blends with co-continuous morphology: Investigating the effects of polymer interface on nanoparticle network stabilization”

This study aimed to investigate the co-continuous morphology of polymer blends and determine whether nanoparticles can be localized at the interface of polymers to create a well-organized network and decrease the percolation threshold. The researchers chose solution-mixed polystyrene (PS)/polymethyl methacrylate (PMMA) blends containing reduced graphene oxide (rGO) for analysis of their rheological, electrical, dynamic-mechanic properties, topography, and morphology. Graphene oxide in varying degrees of thermal reduction was prepared, and surface tension measurements were used to detect the range at which the particles tend to reside at the interface. Based on electrical characterization, it was determined that the required amount of rGO to cover the total polymer interface in the co-continuous blend is approximately 0.1 wt% on a volume basis. The rheology time sweep revealed that, while the initial storage modulus of the nanocomposite containing interface-located particles is similar to that of the sample with randomly distributed particles, the increase in storage modulus over time is less steep, resulting in a lower final value. These findings confirm that the flocculation of rGO particles decreases when they are located at the interface.

Facile Fabrication of Absorption-Dominated Biodegradable Poly(lactic acid)/Polycaprolactone/Multi-Walled Carbon Nanotube Foams towards Electromagnetic Interference Shielding

The use of electromagnetic interference shielding materials in the mitigation of electromagnetic pollution requires a broader perspective, encompassing not only the enhancement of the overall shielding efficiency (SET), but also the distinct emphasis on the contribution of the absorption shielding efficiency within the total shielding efficiency (SEA/SET). The development of lightweight, biodegradable electromagnetic interference shielding materials with dominant absorption mechanisms is of paramount importance in reducing electromagnetic pollution and the environmental impact. This study presents a successful fabrication strategy for a poly(lactic acid)/polycaprolactone/multi-walled carbon nanotube (PCL/PLA/MWCNT) composite foam, featuring a uniform porous structure. In this approach, melt mixing is combined with particle leaching techniques to create a co-continuous phase morphology when PCL and PLA are present in equal mass ratios. The MWCNT is selectively dispersed within the PCL matrix, which facilitates the formation of a robust conductive network within this morphology. In addition, the addition of the MWCNT content reduces the size of the phase domain in the PCL/PLA/MWCNT composite, showing an adept ability to construct a compact and stable conductive network. Based on its porous architecture and continuous conductive network, the composite foam with an 80% porosity and 7 wt% MWCNT content manifests an exceptional EMI shielding performance. The SET, specific SET, and SEA/SET values achieved are 22.88 dB, 88.68 dB·cm3/g, and 85.80%, respectively. Additionally, the resulting composite foams exhibit a certain resistance to compression-induced deformations. In summary, this study introduces a practical solution that facilitates the production of absorption-dominated, lightweight, and biodegradable EMI shielding materials at scale.

Polymerization Induced Microphase Separation for the Fabrication of Nanostructured Materials.

Polymerization induced microphase separation (PIMS) is a strategy used to develop unique nanostructures with highly useful morphologies through the microphase separation of emergent block copolymers during polymerization. In this process, nanostructures are formed with at least two chemically independent domains, where at least one domain is composed of a robust crosslinked polymer. Crucially, this synthetically simple method is readily used to develop nanostructured materials with the highly coveted co-continuous morphology, which can also be converted into mesoporous materials by selective etching of one domain. As PIMS exploits a block copolymer microphase separation mechanism, the size of each domain can be tightly controlled by modifying the size of block copolymer precursors, thus providing unparalleled control over nanostructure and resultant mesopore sizes. Since its inception 11 years ago, PIMS has been used to develop a vast inventory of advanced materials for an extensive range of applications including biomedical devices, ion exchange membranes, lithium-ion batteries, catalysis, 3D printing, and fluorescence-based sensors, among many others. In this review, we provide a comprehensive overview of the PIMS process, summarize latest developments in PIMS chemistry, and discuss its utility in a wide variety of relevant applications.

Effect of steady shear deformation on electrically conductive PP/PS/MWCNT composites

Conductive polymeric materials are commonly obtained by adding conductive nanoparticles to blends of immiscible polymers that form a cocontinuous morphology. However, during processing, morphology changes, affecting material properties. This study investigates the impact of steady shear deformation on the morphological and electrical properties of a model system consisting of polypropylene/polystyrene/multiwall carbon nanotubes (MWCNTs). The findings reveal that the deformation results in the coarsening of the blend morphology and disruption of the electrical network, increasing both the rheological and electrical percolation threshold concentrations. The evolution of both electrical and morphological properties depends on MWCNT concentration, strain amplitude, and shear rate. The MWCNT concentration, below a certain level, leads to a disruption in electrical conductivity at high shear rates. However, if the MWCNT concentration is above 1 wt. %, the balance between filler network breakup and nanoparticle diffusion is maintained, resulting in stable electrical conductivity and morphology.

Preparation and properties of double percolated co-continuous PC/PET/MWCNT/GNP engineering polymer blend nanocomposites

This study reports on the preparation and characterization of nanocomposites based on polycarbonate (PC)/poly ethylene terephthalate (PET) blend containing low amounts of hybrid of multiwalled carbon nanotube (MWCNTs) and graphene nanoplates (GNPs) by melt mixing. To use double percolation mechanism, at first a co-continuous polymer blend was prepared and the influence of nanofiller content on morphology, electrical conductivity, rheological and mechanical properties of co-continuous PC/PET blend was investigated. Blend containing 60 wt. % PET showed co-continuous morphology as observed by scanning electron microscopy and it was found that co-continuity remained unchanged by the addition of nanofillers. The direct current (DC) electrical conductivity results showed a low electrical percolation threshold around 0.5 phr. The results obtained from differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) showed an increase in thermal stability and crystallinity of nanocomposites. By increasing nanofiller amount, the storage modulus, loss modulus, and complex viscosity of samples increased as an indication of the strong network formation between nanofillers and polymer chains. The rheological percolation threshold was also found in the range of 2.5–3.5 phr of nanofillers. The tensile measurements results showed that the addition PC to PET increases the tensile strength of PET.

Thermal and tribo-mechanical properties of high-performance poly(etheretherketone)/reduced graphene oxide nanocomposite coatings prepared by electrophoretic deposition

The thermal stability and degradation, near-to-surface mechanical properties, and scratch resistance and damage mechanism of poly(etheretherketone) (PEEK)/reduced graphene oxide (RGO) nanocomposite coatings are analyzed and discussed in terms of their nanosheet content and microstructure. Although RGO modified the thermal stability and degradation of the polymeric matrix, for instance, by slightly reducing the onset degradation temperature, its addition was not a limiting factor in the PEEK processing. Respecting the microstructural features induced by the nanosheets, the nanocomposite coatings were found to exhibit (i) a partially exfoliated and large-scale co-continuous morphology related to RGO nanosheets whose basal planes were mainly aligned with the coating surface, (ii) a dendritic morphology of PEEK domains related to transcrystallinity, (iii) and irregular domains associated with the deposition of PEEK particles wrapped by the nanosheets. The changes provoked by RGO in the morphology and PEEK crystalline phase influenced the near-to-surface mechanical properties, scratch resistance, and scratch damage mechanism of the nanocomposite coatings. Within this context, the interlayer strength between the nanosheets in the large-scale co-continuous morphology and PEEK transcrystallinity had an important effect. Furthermore, the random-bumpy surface texture formed by the irregular PEEK domains together with the conformal cracking damage mechanism was decisive in the scratch response of the PEEK/RGO nanocomposite coatings. The comprehensive characterization carried out in this work concludes that PEEK/RGO electrophoretic coatings are suitable for a variety of applications requiring tribo-mechanical resistance.Graphical

Particle-size dependent stability of co-continuous polymer blends

The properties of polymer blend nanocomposites are typically associated with spatiotemporal distribution of nanoparticles within a polymer blend system. Here, we present in situ high-temperature confocal rheology studies to assess the effect of particle size on the extent of particle agglomeration, particle migration, and subsequently their influence on the coarsening dynamics of polymer blends filled with pristine silica particles. We investigate co-continuous polypropylene-poly(ethylene-co-vinyl acetate) blends filled with five different silica particles with a diameter ranging from 5 to 490 nm. While particle size does not play a role when particles are thermodynamically driven to their preferred polymer phase, a striking effect is achieved when particles are kinetically trapped at the interface. We find that the interparticle interaction largely driven by size dependent long-range repulsive forces governs their extent of agglomeration, severely affecting their ability to stabilize co-continuous morphology. Strikingly, the largest (490 nm) particles are more effective in suppressing coarsening than 5 nm particles, while 140 and 250 nm particles are found to be the most effective. We demonstrate that kinetic trapping of primary particles of either size is influenced by the interplay of interfacial folding during melt blending and Laplacian pressure exerted at the interface. These results extend our fundamental understanding of the stabilization of co-continuous morphology in polymer blends by particles.

Polymer blend particles with dual-phase morphology prepared using a novel one-pot method via a phase inversion emulsion procedure

We develop a new method for preparing polymer blend particles with dual-phase morphology based on a phase inversion emulsion process. Using this method, the polystyrene (PS)/ethylene–vinyl acetate (EVA) copolymer particles were prepared and analyzed. The preparation procedure included a emulsification of liquid styrene monomer with dissolved EVA and a following free radical polymerization to convert the monomer droplets into solid blend particles.The obtained PS/EVA particles had a dual-phase morphology. With increasing EVA content, the structure of EVA dispersed in PS matrix switched from spherical, stripe to nearly co-continuous morphology and the particles become significantly tougher and the maximum impact strength reached 9.13 KJ/m2. This method provides the opportunity to prepare a number of new kinds of polymer blend particles with tailored performance even though the composed polymers are condensation polymers or unreachable at atmospheric pressure.

The cocontinuous morphology induced from the graphene nanosheets percolation network structures in the immiscible high density polyethylene/polyamide 6/graphene nanosheets composites

AbstractThe addition of graphene nanosheets (GNSs) into immiscible polymer composites to induce the cocontinuous morphologies shows potential application in reinforced nanocomposites and conductive polymer nanocomposites. In this work, immiscible high density polyethylene (HDPE)/polyamide 6 (PA6)/GNS composites were prepared via melt mixing. The electrical and rheological property of HDPE/PA6 composites filled with various GNS contents according to different viscosity ratios and mixing orders were investigated to reveal the double percolation effect via percolation scaling laws, and compared with those of HDPE/GNS and PA6/GNS composites. The morphology and GNS dispersion state of HDPE/PA6/GNS composites were examined via transmission electron microscopy and scanning electron microscope. Most of the GNS were selectively located in the PA6 phase of HDPE/PA6/GNS composites. The GNS‐related network and mixing order played important roles in the cocontinuous morphology formation and performance of HDPE/PA6/GNS conductive composites. Moreover, the addition of GNS also affected the crystallization kinetics and mechanical property of HDPE/PA6/GNS composites.

Relationship Between The Co-Continuous Morphology of Immiscible Polymer Blends and the Structure of An In Situ Formed Graft Copolymer.

Suitable compatibilizers are essential to prepare immiscible polymer blends with stable co-continuous morphologies. From the thermodynamic point of view, such compatibilizer should not only reduce the interfacial tension, but also promote the formation of flat interface between different phases. Meanwhile, it must not hinder the coalescence of dispersed phase. Therefore, asymmetric structures are required for those block or graft copolymer compatibilizers. However, from the kinetic point of view, copolymers with asymmetric structures are prone to be dragged out from the interface and form micelles in one phase under the processing conditions, which will lose their compatibilization effects. The balance between such thermodynamic and kinetic factors remains unclear. In this paper, the relationship between the morphology of the compatibilized polystyrene/nylon 6/styrene-maleic anhydride copolymers (PS/PA6/SMA) immiscible polymer blends and the structures of the in-situ formed SMA-g-PA6 graft copolymers as well as the processing conditions are studied. Two kinds of SMA are used as compatibilizers: SMA28 (Mw = 110,000g/mol, MAH content 28wt.%) and SMA11 (Mw = 110,000g/mol, MAH content 11wt.%). After melt blending with PA6 into an internal mixer, the in-situ formed copolymer SMA28-g-PA6 has an average four PA6 side chains grafted on one SMA backbone, while that of SMA11-g-PA6 has only one PA6 side chain. Dissipative particle dynamics (DPD) simulation results indicate that both SMA28-g-PA6 copolymer and PS/PA6/SMA28 blends tend to form co-continuous structure, while SMA11-g-PA6 copolymer and PS/PA6/SMA11 blends form sea-island morphologies. However, these results are confirmed experimentally only at relatively low rotor speed of the internal mixer (60rpm). When the rotor speed of the mixer is higher (105rpm), sea-island morphologies are obtained in PS/PA6/SMA28 blends and co-continuous ones are found in PS/PA6/SMA11 systems. These results indicate that higher shear stress will favor to elongate the minor phase domains and form flat interfaces, which is benefit for the formation of co-continuous morphologies; meanwhile, high shear stress may pull the graft copolymers with asymmetric structures (SMA28-g-PA6) out from the interface of PS and PA6 and induce the formation of sea island morphologies. This article is protected by copyright. All rights reserved.

Tailored distribution of 1D nanoparticles in co-continuous EMA/TPO flexible polymeric blends used as emerging materials for suppressing electromagnetic radiation

Electromagnetic interference (EMI) is unwanted noise or interference that often affects electronic equipment and human health. An effective EMI shielding material is needed to protect electronic equipment and human health to block EMI signals. In this work, we have developed electrically conductive polymer composites via the preferential localization of MWCNTs in a co-continuous ethylene-co-methyl acrylate (EMA)/thermoplastic polyolefin (TPO) (80/20 w/w) binary blend system using a solution mixing technique. The electrical percolation threshold was achieved by incorporating 3 to 5 wt% of MWCNT in the blend matrix. FESEM and TEM images indicated a co-continuous morphology in which MWCNT was thermodynamically and kinetically driven into the EMA phase of the polymer blend. The DC and AC conductivity of the fabricated composite was significantly increased upon loading the MWCNT in the polymer composite. A total EMI shielding effectiveness of −35 dB was achieved by adding 15 wt% MWCNT into the matrix in the frequency range of 14.5–20.0 GHz, along with good thermal conductivity, dielectric properties, and mechanical properties.