Polyamide 11/Poly(vinylidene fluoride) Blends as Novel Flexible Materials for Capacitors

A novel capacitor with high dielectric constant (ε) has been developed by blending poly(vinylidene fluoride) (PVDF) with polyamide (PA11). The blends show high dielectric constants (ε_blend = 40), which give better frequency stability (1 MHz), and excellent mechanical properties. Based on certain volume fractions, the measured dielectric constants (ε _blend ) were found to exceed those of the corresponding polymers, in contrasted to conventional composites, where ε_polymerA < ε_composite < ε_polymerB. SEM investigations suggest that the enhanced dielectric behavior originates from significant interfacial polymer‐polymer interactions. DSC and XRD demonstrate that blending PA11 with PVDF affects the crystalline behavior of each component. However, the PA11/PVDF blends exhibit a slightly high dielectric loss (tanδ ≈ 0.17), which is a great disadvantage to a capacitor. Adding a copolymer of styrene and maleic anhydride decreased the dielectric loss (tanδ ≈ 0.057) and increased the dielectric constant (ε_blend = 60). Our findings suggest that the high‐ε polymeric blends created represent a novel type of material that is flexible and easy to process, of relatively high dielectric constant, of high breakdown strength and, moreover, is suited to applications in flexible electronics.

     

Largely enhanced ductility of immiscible high density polyethylene/polyamide 6 blends via nano‐bridge effect of functionalized multiwalled carbon nanotubes

Immiscible polymer blends usually exhibit negative deviation in mechanical properties compared with the corresponding pure polymers due to the weak interfacial bonding between the two polymers. Due to the bridge effect of the oriented carbon nanotubes (CNTs) on the craze and crack development at the load of stress, CNTs have been proved to be efficient toughening agent for polymers. In this work, functionalized multiwalled carbon nanotubes (FMWCNTs) have been introduced into immiscible high density polyethylene/polyamide 6 (HDPE/PA6) blends through different sample preparation methods. The mechanical measurements demonstrate that, when the nanocomposite is prepared from the HDPE master batch, the sample exhibits excellent tensile strength and toughness simultaneously. For all the nanocomposites, FMWCNTs tend to migrate and/or maintain in PA6 particles, leading to the variation of the crystallization behavior in PA6 phase. Further results based on morphologies characterization indicate that the intensified interfacial adhesion between HDPE and PA6, which is realized by the nano‐bridge effect of FMWCNTs in the interfaces, is the main reason for the largely improved ductility. Copyright © 2010 John Wiley & Sons, Ltd.     

In situ fibrillation of polyamide 6 in isotactic polypropylene occurring in the laminating‐multiplying die

The polyamide 6 (PA6)/isotactic polypropylene (iPP) in situ fibrillation composites are prepared by a novel extrusion die with an assembly of laminating‐multiplying elements (LMEs). The scanning electron micrographs illustrate that the dividing‐multiplying processes in LMEs elongate, break, and stabilize the dispersed PA6 phase in the iPP matrix along the flowing direction (FD). The morphology development of PA6 with different LME numbers greatly affects the rheological properties, crystalline behaviors, and mechanical properties. The dynamic rheological test performed at 195°C shows that the increased spatial restriction of the high‐aspect‐ratio PA6 particles increases the viscoelastic moduli, complex viscosity, and relaxation time. The crystalline analysis reveals that the heterogeneous nucleation becomes predominant and the transcrystalline morphology is observed in those samples produced by more LMEs. The tensile tests indicate that both, breaking strength and elongation, enhanced simultaneously because of the fibrillation of dispersed phase and the improvement in interfacial adhesion between the fibers and the matrix. Copyright © 2009 John Wiley & Sons, Ltd.     

Experimental validation of an effective carbon number-based approach for the gas chromatography–mass spectrometry quantification of ‘compounds lacking authentic standards or surrogates’

For the quantitative analysis of ‘compounds lacking authentic standards or surrogates’ (CLASS) in environmental media, we previously introduced an effective carbon number (ECN) approach to develop an empirical equation for the prediction of their response factor (RF). In this research, a series of laboratory experiments were carried out to benchmark the reliability of an ECN approach for sorbent tube/thermal desorption/gas chromatography (GC)/mass spectrometry (MS) applications. First, the ECN values were determined using external calibration data from 25 reference volatile organic compounds (VOCs) using two MS dectectors (quadrupole (Q) and time-of-flight (TOF)). Then, a certified standard mixture of 54 VOCs was analyzed by each system as a simulated unknown sample. The analytical bias, assessed in terms of percentage difference (PD) between the certified and ECN-predicted mass values, averaged 19.2 ± 16.1% (TOF-MS) and 28.2 ± 27.6% (Q-MS). The bias using a more simplified carbon number (CN)-based prediction increased considerably, yielding 53.4 ± 53.3% (TOF-MS) and 61.7 ± 81.3% (Q-MS). However, the bias obtained using the ECN-based prediction decreased significantly to yield average PD values of 9.84 ± 7.28% (TOF-MS) and 16.8 ± 8.35% (Q-MS), if the comparison was limited to 26 (out of 54) VOCs with CN ≥ 4 (i.e., 25 aromatics and hexachlorobutadiene).     

Influence of relative humidity and loading frequency on the PA6.6 thermomechanical cyclic behavior: Part II. Energy aspects

In this study, we investigated the influence of relative humidity (RH) and loading rate on the energy response of PA6.6 matrix specimens. The latter were subjected to oligocyclic tensile-tensile tests at 3 different RH and 2 loading rates. Infrared thermography was used to obtain a direct estimate of heat sources using the heat diffusion equation. Using the mechanical and thermal responses discussed in the first part of this work, complete energy rate balances were drawn up. In particular, the time courses of deformation, and dissipated and stored energy rates are discussed. The strong influence of the loading frequency and RH on the energy storage mechanisms is also highlighted.     

Surface antimicrobial modification of polyamide by poly(hexamethylene guanidine) hydrochloride

Antimicrobial polyamide (PA) received much attention for the demand of packaging and biomedical fields. In this paper, an antimicrobial PA6 membrane was prepared via a surface chemical reaction. A highly effective antibacterial component (PHMG‐E) with terminal epoxy group was firstly synthesized via a reaction between polyhexamethylene guanidine hydrochloride (PHMG) and ethylene glycol diglycidyl ether (EGDE). Then, PHMG‐E was bonded on the surface of PA6 membrane with secondary amine reduced by borane‐tetrahydrofuran (BH₃‐THF). The antimicrobial rates of surface‐modified PA6 membrane (PA6‐PHMG) against Escherichia coli and Staphylococcus aureus were both higher than 99.99%, and the PHMG was non‐leaching due to the chemical bonding. The hydrophilicity of antibacterial PA6 membrane was also significantly improved and the mechanical performance became better.     

Speciation of aluminium fluoride complexes and Al in soils from the vicinity of an aluminium smelter plant by hyphenated High Performance Ion Chromatography Flame Atomic Absorption Spectrometry technique

The paper presents a new tool for the determination of inorganic speciation forms of aluminium: AlF_n^{(3 − n)+}, and Al³⁺ by means of the HPIC-FAAS. The proposed method has been successfully used for speciation analysis (qualitative and quantitative) of inorganic aluminium forms AlF_n^{(3 − n)+} in soil samples. In order to isolate the most environmentally available fraction, 5 g of the sample was collected and extracted in deionised water (water soluble fraction) for 1 h using a magnetic stirrer. The determinations in a hyphenated technique system were performed for a number of prepared water extracts. Concentration determinations of particular aluminium forms were performed based on model studies and real samples. The separation of Al species with nominal charge of + 1, + 2, and + 3 required a run time of less than 4 min during a single analysis. Based on the analysis of water extracts of soil, it was obtained that aluminium forms elute in the following order: 1PA (first signal) — AlF₂⁺ and/or AlF₄⁻; 2PA (second signal) — AlF²⁺ and/or AlF₃⁰; 3PA (third signal) — Al³⁺. In order to confirm the occurrence of these forms a simulation using the Mineql program was conducted. The details of speciation analysis of aluminium fluoride forms by means of an HPIC-FAAS instrument equipped are presented. Interpretation of the speciation analysis of the water soluble fraction of soil samples is proposed, based on the separation during chromatographic run and calculated data by Mineql.     

Comparative study of kinetics isomerization of substituted polyacetylene (Cl,F and I): Ab initio and DFT calculations

Ab initio and DFT methods were used to investigate the interconversions of substituted polyacetylene conformers C₁₀H₆X₆ (X=F, Cl and I) in the vapour phase. The rates of this geometrical isomerization have been calculated and the Arrhenius parameters evaluated. In the case of unsubstituted polyacetylene as the reference, the B3LYP Arrhenius parameters obtained are A₁=2.99 × 10¹⁷ s^–1 and E_a=17.30 kcal mol^–1. The values of the equilibrium constant for the reaction have also been determined at various temperatures between 300 and 500 K and the value of the energies change calculated. The results also suggest that the straightforward kinetics characterizing the majority of substituted polyacetylene isomerizations above 300 K. The isomerization energies are positive and the barrier heights ΔE_barrier are expected to be sensitive for the magnitude of halogens effects. According to geometries features the Cis → Trans isomerization in the gas phase occurs by a rotational mechanism.     

Phosphorylated silica/polyamide 6 nanocomposites synthesis by in situ sol–gel method in molten conditions: Impact on the fire-retardancy

Polyamide 6 (PA6)/phosphorylated silica nanocomposites were synthesized during PA6 extrusion through in situ formation of the inorganic phase without solvent. This synthesis is based on the hydrolysis-condensation reactions of diethylphosphatoethyltriethoxysilane (SiP) as a functional inorganic precursor in combination with or without tetraethoxysilane (TEOS) dispersed in the molten PA6. This synthesis is carried out during PA 6 matrix extrusion that means at high temperature and under shear. The characterization of the in situ synthesized PA6/phosphorylated silica nanocomposites by solid ²⁹Si Nuclear Magnetic Resonance (NMR), Small Angle X-ray Scattering (SAXS) and Transmission Electron Microscopy (TEM) coupled with Energy Dispersive X-ray spectroscopy (EDX) demonstrated the possibility to directly create in less than 5 min at 220 °C a phosphorylated silica uniformly dispersed in the PA6, i.e. in the form of well dispersed particles or aggregates of sub-micron range. The influence of silicon and phosphorus on the thermal and fire retardant behaviour was investigated by thermogravimetric analysis (TGA), cone calorimeter and UL94 tests. The fire retardant behaviour was modified with a formation of a char and a peak heat release rate (PHRR) decrease by more than 50% for the SiP based nanocomposite compared to the pure PA6.     

Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability,mechanical properties and surface resistivity

In this paper, polyvinyl alcohol/phytic acid polymer (PVA/PA polymer) was synthesized through esterification reaction of PVA and PA in the case of acidity and ultrasound irradiation and characterized, and PVA/PA polymer film was prepared by PVA/PA polymer and characterized, and the influence of dosage of PA on the thermal stability, mechanical properties and surface resistivity of PVA/PA polymer film were researched, and the influence of sonication time on the mechanical properties of PVA/PA polymer film was investigated. Based on those, it was concluded that the hydroxyl group on the chain of PVA and the phosphonic group on PA were connected together in the form of phosphonate bond, and the hydroxyl group on the chain of PVA were connected together in the form of ether bond after the intermolecular dehydration; in the meantime, it was also confirmed that PVA/PA polymer film prepared from 1.20 mL of PA not only had the high thermal stability and favorable ductility but also the low surface resistivity in comparison with PVA/PA polymer film with 0.00 mL of PA, and the ductility of PVA/PA polymer film was very sensitive to the sonication time.