In situ Lubrication Dispersion of Multi‐Walled Carbon Nanotubes in Poly(propylene) Melts

An in situ lubrication dispersion method is developed to achieve electrical conductivity in PP containing a small amount of MWCNTs. Good dispersion of the MWCNTs in PP is observed even after a short mixing time because the interactions between the entangled nanotubes are reduced. By in situ lubrication dispersion, the electrical percolation threshold of the PP nanocomposite can be as low as 0.5–0.7 wt% MWCNT. Rheological data also support percolation at 0.5 wt% MWCNT. With 0.5 wt% MWCNT, the slope of G′ at low frequency approaches unity and shows non‐terminal behavior. The proposed dispersion method enhances the wetting of MWCNTs and improves MWCNT dispersion compared to both direct mixing of MWCNT powder with a polymer melt and conventional master batch dilution.

     

Direct Melt Extrusion Processing of Nylon 6/Clay Nanocomposites Based on Pristine Montmorillonite

Summary: An original direct melt extrusion processing of nylon 6/clay nanocomposites was reported based on pristine (Na⁺‐based) montmorillonite as well as a simple approach using a typical two‐screw extruder. By the application of intercalation agents as the thermodynamic assistants, this method is as an appropriate procedure for industrialized manufacture together with much lowered production cost. Interestingly enough, the synergistic effects of montmorillonite with other inorganic particulates was observed for the first time here.

X‐ray diffraction patterns of pristine MMT and nylon 6/MMT composites with grouped intercalation agents.     

Influence of Screw Speed on Electrical and Rheological Percolation of Melt‐Mixed High‐Impact Polystyrene/MWCNT Nanocomposites

The influence of screw speed on the electrical and rheological percolation of HIPS/MWCNT composites prepared via melt mixing was investigated. Microscopic examination of these composites using POM, FESEM and HRTEM revealed optimum MWCNT dispersion was achieved at intermediate screw speeds. On addition of MWCNTs to HIPS, the electrical conductivity of HIPS increased by up to 12 orders of magnitude. At screw speeds up to 100 rpm an electrical percolation of 1–3 wt.‐% was achieved. This increased to 3–5 wt.‐% when the screw speed was increased to 150 rpm. The onset of a rheological percolation was detected for an MWCNT loading of 5 wt.‐%, irrespective of screw speed employed. An up‐shift in the Raman G‐band of 24 cm^?1 was observed, implying strong interfacial interaction between HIPS and MWCNTs.

     

Morphological Characterization of PMMA/PAN Composite Particles in Nano to Submicro Size

Summary: It is necessary to use a selective staining agent to enhance image contrast for transmission electron microscopy (TEM) morphological characterization of polymer composite particles. However, the typical selective staining agents osmium tetraoxide and ruthenium tetraoxide are neither suitable for poly(methyl methacrylate) (PMMA)/polyacrylonitrile (PAN) composite particles. In this study, it was found that phosphotungstic acid (PTA) solution with 6.4 pH value is unsuitable for PMMA, but it can stain PAN. Therefore, it can be a selective staining agent in the TEM for PMMA/PAN composite particles. By controlling different thermodynamic and kinetic polymerization parameters, PMMA/PAN and PMMA/P(AN‐MMA) composite particles with nano to submicro sizes having different morphological structures were synthesized. TEM micrographs of all these composite particles with their predicted morphology have been compared, and the experimental results are completely consistent with the predictions.

TEM micrograph of PMMA/PAN composite particles.     

Ternary Poly(styrene‐co‐acrylonitrile)/Poly(vinyl chloride) Blend Composites with Multi‐Walled Carbon Nanotubes and Enhanced Physical Characteristics

We report a ternary system of poly(styrene‐co‐acrylonitrile) (SAN), poly(vinyl chloride) (PVC), and multi‐walled carbon nanotube (MWCNT) composites prepared by both a solution blending method and the SOAM. The MWCNT content in the composites was optimized by both TGA and mechanical characterization of binary mixtures of SAN/MWCNT and PVC/MWCNT composites. The dispersion of MWCNTs in the miscible SAN/PVC blends was characterized by FT‐Raman spectroscopy, FE‐SEM, and FE‐TEM. The distribution of MWCNTs in the SAN/PVC blends was examined in terms of their wetting coefficients and minimization of the interfacial energy. Composites prepared using the SOAM method showed superior physical properties to the SAN/PVC blends and SAN/PVC/MWCNT composites prepared using the solution blending method.

     

Coaxial Electrospinning with Triton X‐100 Solutions as Sheath Fluids for Preparing PAN Nanofibers

Coaxial electrospinning using surfactants as sheath fluid for preparing high‐quality polymer nanofibers is studied. PAN nanofibers are fabricated using this process with Triton X‐100 solutions in DMF. FESEM demonstrates that the Triton X‐100 solution has a significant influence on the quality of the nanofibers. The nanofiber diameters can be controlled by adjusting the concentration of Triton X‐100 in the sheath fluids with a scaling law D = 640 C^?0.32. The mechanism of the influence of Triton X‐100 solutions on the formation of PAN fibers is discussed and it is demonstrated that coaxial electrospinning with surfactant solution is a facile method for achieving high‐quality polymer nanofibers.

     

Epoxy Resin Nanofibers Prepared Using Electrospun Core/Sheath Nanofibers as Templates

A strategy is described to prepare epoxy resin nanofibers by combining coaxial electrospinning and traditional hot‐curing processes. Core/sheath nanofibers with diameters of 480 ± 80 nm are prepared at flow rates of 0.1 and 2 mL h^?1 for the core (20% w/v EP and 6% w/v curing agent in ethanol/acetone) and sheath (10% PVP in ethanol) fluids. After the curing of the nanofibers and selective removal of the sheath PVP, EP nanofibers with an average diameter of 210 ± 60 nm are obtained. ATR‐FTIR analysis shows that the EP nanofibers display no obvious difference compared with an EP film cast from the core solution. The method presented allows to develop functional EP nanoproducts and to prepare heat‐cured resin nanofibers.

     

The Effect of Mold Temperature on the Performance of Injection Molded Poly(lactic acid)‐Based Bioplastic

This research investigates the effects of processing parameters, namely molding temperature on the mechanical performance of impact‐modified poly(lactic acid) (PLA). Polymer crystallization dictates many of the final properties of the material. Increasing the mold temperature, crystallization may progress to a further stage, increasing crystallinity. Molding at a lower temperature, and producing a highly amorphous polymer can increase the mechanical properties, namely elongation and impact strength. Molding at 30 versus 90 °C improved the elongation from 22 to 243% and the impact strength from 67 to 133 J · m^?1. This improvement is not without its drawbacks. By molding at 30 °C, the polymer becomes very amorphous, and thus is more susceptible to unwanted processes such as physical aging.

     

1,8‐Naphthalimides as Blue Emitting Fluorophores for Polymer Materials

The copolymerization of 1,8‐naphthalimide derivatives (as fluorophore) with acrylonitrile has been investigated. The photophysical characteristics of monomeric and polymeric fluorophores in N,N‐dimethylformamide solution have been determined and discussed. During copolymerization, no changes in the chromophoric systems of the fluorophore occur. The influence of the studied monomeric 1,8‐naphthalimide fluorophores upon the structurally bleached polyacrylonitrile has been determined. Infrared absorption characteristics of the polymerizable 4‐alkoxy‐ and 4‐allyloxy‐N‐substituted‐1,8‐naphthalimides have been measured and discussed. The effect of the substituents upon the vibration frequencies of the carbonyl and allylic groups has been established.

Blue fluorescent polyacrylonitrile copolymers with 1,8‐naphthalimides side‐group.     

The Effect of Phase Structure on the Tribological Properties of PA66/HDPE Blends

Summary: In this paper, immiscible, partially miscible and miscible blends of polyamide 66 (PA66) and high density polyethylene (HDPE) were obtained by changing compatibilizer concentrations. Mechanical and tribological properties of materials were tested. It was found that the addition of compatibilizer greatly improved the mechanical properties of PA66/HDPE blends. The wear of PA66/HDPE blends was strongly affected by the phase structure. The best blend for lower friction coefficient and higher wear resistance was the blend with a miscible structure, which significantly improved the tribological properties of PA66 and HDPE. SEM investigations on the worn surface and the steel counterface indicated that, for the immiscible and partially miscible blend systems, the dispersed HDPE particles were pulled out from the worn surfaces during sliding because of the poor adhesion between HDPE and PA66, while this was not observed in the miscible blend system.

SEM micrograph of the worn surface formed by PA66/HDPE blend without HDPE‐g‐MAH.     

Transcrystallinity in Surface Modified Aramid Fiber Reinforced Nylon 66 Composites

Aramid (kevlar‐49) fibers were surface treated by two different methods to induce roughness and then used to produce unidirectional nylon 66 based composites. The transcrystallinity generated around the treated fibers was characterized by SEM and polarized light microscopy and compared with the regular transcrystalline layers produced by pristine aramid under the same processing conditions. The treated fibers generated a double transcrystalline layer, the inner layer being thinner and more compact than the regular nylon 66 transcrystallinity. In addition, mechanical testing of the composites showed the longitudinal Young's modulus of the treated fiber composites to be significantly higher than the control in a wide range of fiber volume fractions.

Polarized light microscopy picture of double transcrystallinity in Br/NH₃ treated aramid fiber reinforced nylon 66.     

Aligned Nafion® Nanocomposites: Preparation and Morphological Characterization

A novel nanocomposite based on Nafion® (ionomer) and a layered silicate is studied. An innovative approach of processing a composite under electric field to induce orientation of the inorganic filler was carried out and accomplished in the present work. The morphology of oriented composites was analyzed by scanning electric potential microscopy (SEPM) and transmission electron microscopy (TEM). Films based on both plain ionomer and composite displayed fine contrast in SEPM, differentiating the phases, which could not be achieved using conventional atomic force microscopy. The orientation of the silicates in the composites is evident from the SEPM picture.

AFM of Nafion®/montmorillonite composite films prepared by solution casting under electric field (Image obtained by SEPM).     

Formation of in situ CB/PET Microfibers in CB/PET/PE Composites by Slit Die Extrusion and Hot Stretching

Summary: In this present study, the in situ fabrication of a microfibrillar composite based on poly(ethylene terephthalate) (PET), polyethylene (PE), and carbon black (CB) is attempted. PET and CB were first melt mixed. The CB/PET compound and PE were subsequently melt extruded through a slit die and then hot stretched. The morphological observation of the as‐stretched extrudate indicated that well‐defined microfibers of CB/PET compound could be generated at appropriate CB contents and a fixed hot stretch ratio. In addition, CB was always selectively located in PET. The microfibrillar CB/PET/PE composite has the potential to be a new electrically conductive polymer composite.

Morphology of the carbon black/poly(ethylene terephthalate)/polyethylene (PE) composite after additional mixing in the mixer at the processing temperature of PE.     

Mechanical Properties of Hemp‐Fibre‐Reinforced Euphorbia Composites

A composite material consisting of hydroxide‐modified hemp fibres and euphorbia resin was produced. The composites were tested in tension, short‐beam interlaminar shear stress and in impact. There was an increase in the tensile strength and modulus for resins with high‐hydroxyl‐group based composites. Similar results were obtained for interlaminar shear stress while low‐hydroxyl group euphorbia resin based composites exhibited high impact strength. The euphorbia resin with high hydroxyl content yielded composites with high stiffness. The use of euphorbia‐based resins in composite manufacture increases the value of the euphorbia oil as well as creating a new route of composite manufacturing.

     

Analysis of Crosslinked Styrene‐Butadiene Rubbers by Liquid Chromatography and FT‐IR Spectroscopy, 1

Crosslinked styrene‐butadiene and butadiene rubbers can efficiently be analyzed by liquid chromatography and FT‐IR spectroscopy. In a first step the vulcanizate is pyrolyzed under mild conditions. The resulting high molar mass fragments are extracted from the bulk material and analyzed by size exclusion chromatography. The molar masses of the extractables are in the range of 3 000 to 25 000 g/mol. The chemical composition as a function of molar mass is visualized by coupled SEC‐FT‐IR spectroscopy. By quantitative analysis of the FT‐IR spectra the concentrations of the different structural units, including styrene, 1,4‐trans‐butadiene, 1,2‐vinylbutadiene, and 1,4‐cis‐butadiene, are determined. It is shown that the chemical composition of the original non‐crosslinked rubbers and the chemical composition of the extractables are rather identical. Therefore, this technique can be used to obtain structural information on rubber formulations even in the case when the material is already vulcanized.

SEC chromatograms of SBR 1712 and the extractables after pyrolysis, stationary phase: SDV linear, mobile phase: THF, detector: ELSD.     

Co(acac)2‐Mediated Radical Polymerization of Acrylonitrile: Control Over Molecular Weights and Copolymerization With Methyl Methacrylate

The cobalt‐mediated radical polymerization of acrylonitrile in DMSO using cobalt (II) acetylacetonate [Co(acac)₂] as mediator is studied. Both the evolution of molecular weight and conversion over time under various conditions are monitored. Molecular weights increase sharply at the beginning of the reaction and subsequently grow linearly with conversion. No branching of the polymer is observed by ¹³C NMR. By a careful design of the reaction parameters, number‐average molecular weights >1.2 · 10⁵ g · mol^?1 with a PDI around 2.4 together with conversions of up to 90% within 24 h are achieved. The copolymerization parameters of acrylonitrile with methyl methacrylate in DMSO at 30 °C are determined using the Kelen‐Tüdõs approach giving r_AN = 0.33, r_MMA = 0.71.

     

The Effect of Disinfection Methods on the Mechanical Properties of Thermoplastic Recyclates

Summary: Increasing environmental concern encourages the development of new ways to recycle medical products. Post‐consumer medical products are suited for recycling because of their life‐span, but used products have to be disinfected before recycling. Therefore, the influence of different disinfection processes during recycling on the processibility and the mechanical properties of thermoplastics was investigated. As disinfection processes, steam disinfection and disinfection with electron beam and gamma radiation were selected. The characterisation of the properties of disinfected recyclates was undertaken for PE and PP from syringes. The melt mass‐flow rate (MFR), the dynamic mechanical properties, the tensile properties and fracture mechanics parameters were examined. A comparison of the results showed that stiffness and strength remain nearly constant, but the deformation and fracture behaviour tends to be influenced. The selection of appropriate disinfection parameters can avoid unnecessary alteration of the properties. Thus, steam disinfection as well as radiation disinfection up to a dose of about 25 kGy are suited for decontaminating used medical products.

Scheme of the influence of different disinfection methods on selected properties of thermoplastic recyclates.     

Polyolefin/Lignosulfonate Blends, 9

Summary: In the present study, the compatibility, properties and degradability of polyolefin/lignin blends have been studied. Blends of three maleic anhydride grafted copolymers of ethylene‐propylene rubbers containing various content of functional groups with epoxy‐modified lignosulfonate have been investigated by microscopy, X‐ray diffraction, surface and mechanical indices determination, electron spin resonance, IR spectroscopy, differential scanning calorimetry and thermogravimetry. To assess the environmental degradation characteristics, the behavior of the blends during soil burial test has been investigated. The influence of the buried polymer blends on the physiological vegetative processes of the Vicia X Hybrida hort plant has been monitored.

Optical microscopy images of blend EP‐g‐MA 0.3/5 LER, undegraded (left) and degraded (right).     

Thermo‐Physical and Impact Properties of Epoxy Containing Epoxidized Linseed Oil, 1

Summary: Biobased neat epoxy materials containing epoxidized linseed oil (ELO) were processed with an anhydride curing agent. A defined amount of the diglycidyl ether of bisphenol F (DGEBF) was replaced by ELO. The selection of the DGEBF, ELO, and an anhydride curing agent resulted in an excellent combination, to provide a new biobased epoxy material showing high elastic modulus, high glass transition temperature, and high heat distortion temperature (HDT) with larger amounts of ELO. The Izod impact strength was almost constant while changing the amount of ELO. This is a promising result for future industrial applications in different engineering industries.

The effect of changing ELO concentration of the anhydride‐cured neat epoxy on the storage modulus.     

Polymeric Toughening of Particle Filled Cyanate Ester Composites

Summary: The present study examines the effect of polymeric tougheners on the performance of silica filled cyanate ester composites. The polymeric tougheners used have been shown to enhance cyanate ester tougheners in binary toughener/matrix systems. Tougheners that were able to form a favourable phase‐separated morphology resulted in the greatest increase in crack resistance. The addition of these tougheners resulted in minimal loss of strength, and a slight decrease in modulus. Importantly the viscosity of the compounded systems was low enough for them to be readily processable. Whilst conserving most secondary properties, toughener addition did result in a slight increase in composite hydrolytic degradation. This issue was linked to the additive/ additive compounding processes. Removal of this extra moisture should eliminate this concern, permitting the used of these composites in electronic applications.

Effect of ETBN content on the crack resistance of particle filled cyanate ester composites and SEM image of 15 matrix wt.‐% ETBN.