Miscibility, crystallization κinetics and real-time small-Angle x-ray scattering investigation of the semicrystalline morphology in thermosetting polymer blends of epoxy resin and poly(ethylene oxide)

Thermosetting polymer blends of poly(ethylene oxide) (PEO) and bisphenol-A-type epoxy resin (ER) were prepared using 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) as curing agent. The miscibility and crystallization behavior of MCDEA-cured ER/PEO blends were investigated by differential scanning calorimetry (DSC). The existence of a single composition-dependent glass transition temperature (Tg) indicates that PEO is completely miscible with MCDEA-cured ER in the melt and in the amorphous state over the entire composition range. Fourier-transform infrared (FTIR) investigations indicated hydrogen-bonding interaction between the hydroxyl groups of MCDEA-cured ER and the ether oxygens of PEO in the blends, which is an important driving force for the miscibility of the blends. The average strength of the hydrogen bond in the cured ER/PEO blends is higher than in the pure MCDEA-cured ER. Crystallization kinetics of PEO from the melt is strongly influenced by the blend composition and the crystallization temperature. At high conversion, the time dependence of the relative degree of crystallinity deviated from the Avrami equation. The addition of a non-crystallizable ER component into PEO causes a depression of both the overall crystallization rate and the melting temperature. The surface free energy of folding σe displays a minimum with variation of composition. The spherulitic morphology of PEO in the ER/PEO blends exhibits typical characteristics of miscible crystalline/amorphous blends, and the PEO spherulites in the blends are always completely volume-filling. Real-time small-angle X-ray scattering (SAXS) experiments reveal that the long period L increases drastically with increasing ER content at the same temperatures. The amorphous cured ER component segregates interlamellarly during the crystallization process of PEO because of the low chain mobility of the cured ER. A model describing the semicrystalline morphology of MCDEA-cured ER/PEO blends is proposed based on the SAXS results. The semicrystalline morphology is a stack of crystalline lamellae; the amorphous fraction of PEO, the branched ER chains and imperfect ER network are located between PEO lamellae.

Transport and phase dynamics of poly(vinyl pyrrolidone) doped plastically crystalline N-methyl-N-propylpyrrolidinium tetrafluoroborate

The plastic crystal phase forming N-methyl-N-propylpyrrolidinium tetrafluoroborate organic salt (P₁₃BF₄) was combined with 2, 5 and 10 wt.% poly(vinyl pyrrolidone) (PVP). The ternary 2 wt.% PVP/2 wt.% LiBF₄/P₁₃BF₄ was also investigated. Thermal analysis, conductivity, optical thermomicroscopy, and Nuclear Magnetic Resonance (¹¹B, ¹⁹F, ¹H, ⁷Li) were used to probe the fundamental transport processes. Both the onset of phase I and the final melting temperature were reduced with increasing additions of PVP. Conductivity in phase I was 2.6 × 10^{− 4} S cm^{− 1} 5.2 × 10^{− 4} S cm^{− 1} 1.1 × 10^{− 4} S cm^{− 1} and 3.9 × 10− 5 S cm− 1 for 0, 2, 5 and 10 wt.%PVP/P₁₃BF₄, respectively. Doping with 2 wt.% LiBF₄ increased the conductivity by up to an order of magnitude in phase II. Further additions of 2 wt.% PVP slightly reduced the conductivity, although it remained higher than for pure P₁₃BF₄.

Study on the oriented recrystallization of carbon-coated polyethylene oriented ultrathin films

It is confirmed that a layer of vacuum-evaporated carbon on the surface of a preoriented ultrathin polymer film can lead to an oriented recrystallization of the polymer film. This has been attributed to a strong fixing effect of vacuum-evaporated carbon layer on the film surface of the polymer. To study the origin of the strong fixing effect of vacuum-evaporated carbon layer on the polymer films, the melting and recrystallization behaviors of the preoriented ultrathin PE film with a vacuum-evaporated carbon layer were studied by using atomic force microscopy, electron diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. We found that there exists some extent of chain orientation of carbon-coated polyethylene (PE) preoriented ultrathin film above its melting temperature. These oriented PE chain sequences act as nucleation sites and induce the oriented recrystallization of preoriented PE film from melt. Raman spectroscopy results suggest that new carbon-carbon bonds between the carbon layer and the oriented PE film are created during the process of vacuum carbon evaporation. As a result, some of the PE chain stems are fixed to the coated carbon substrate via covalent bond. Such a bonding has retarded the relaxation of the PE chains at the spot and, therefore, preserves the original orientation of the PE stems at high temperature, which in turn derives the recrystallization of the PE chains in an oriented structure.

Electrochemiluminescent monomers for solid support syntheses of Ru(II)-PNA bioconjugates : multimodal biosensing tools with enhanced duplex stability

The feasibility of devising a solid support mediated approach to multimodal Ru(II)-peptide nucleic acid (PNA) oligomers is explored. Three Ru(II)-PNA-like monomers, [Ru(bpy)2(Cpp-L-PNA-OH)]2+ (M1), [Ru(phen)2(Cpp-L-PNA-OH)]2+ (M2), and [Ru(dppz)2(Cpp-L-PNA-OH)]2+ (M3) (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine, Cpp-L-PNA-OH = [2-(N-9-fluorenylmethoxycarbonyl)aminoethyl]-N-[6-(2-(pyridin-2yl)pyrimidine-4-carboxamido)hexanoyl]-glycine), have been synthesized as building blocks for Ru(II)-PNA oligomers and characterized by IR and 1H NMR spectroscopy, mass spectrometry, electrochemistry and elemental analysis. As a proof of principle, M1 was incorporated on the solid phase within the PNA sequences H-g-c-a-a-t-a-a-a-a-Lys-NH2 (PNA1) and H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-lys-NH2 (PNA4) to give PNA2 (H-g-c-a-a-t-a-a-a-a-M1-lys-NH2) and PNA3 (H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-M1-lys-NH2), respectively. The two Ru(II)-PNA oligomers, PNA2 and PNA3, displayed a metal to ligand charge transfer (MLCT) transition band centered around 445 nm and an emission maximum at about 680 nm following 450 nm excitation in aqueous solutions (10 mM PBS, pH 7.4). The absorption and emission response of the duplexes formed with the cDNA strand (DNA: 5′-T-T-T-T-T-T-T-A-T-T-G-C-T-T-T-3′) showed no major variations, suggesting that the electronic properties of the Ru(II) complexes are largely unaffected by hybridization. The thermal stability of the PNA·DNA duplexes, as evaluated from UV melting experiments, is enhanced compared to the corresponding nonmetalated duplexes. The melting temperature (Tm) was almost 8 °C higher for PNA2·DNA duplex, and 4 °C for PNA3·DNA duplex, with the stabilization attributed to the electrostatic interaction between the cationic residues (Ru(II) unit and positively charged lysine/arginine) and the polyanionic DNA backbone. In presence of tripropylamine (TPA) as co-reactant, PNA2, PNA3, PNA2·DNA and PNA3·DNA displayed strong electrochemiluminescence (ECL) signals even at submicromolar concentrations. Importantly, the combination of spectrochemical, thermal and ECL properties possessed by the Ru(II)-PNA sequences offer an elegant approach for the design of highly sensitive multimodal biosensing tools.

Method for determining reaction rate of mild steel containers during melting of magnesium-aluminium alloys and effect of aluminium content on directionally solidified microstructures

A magnesium alloy of eutectic composition (33 wt-'%Al) was directionally solidified in mild steel tubes at two growth rates, 32 and 580 mum s(-1,) in a temperature gradient between 10 and 20 K mm(-1). After directional solidification, the composition of each specimen varied dramatically, from 32'%Al in the region that had remained solid to 18%Al (32 mum s(-1) specimen) and 13%Al (580 mum s(-1) specimen) at the plane that had been quenched from the eutectic temperature. As the aluminium content decreased, the microstructure contained an increasing volume fraction of primary magnesium dendrites and the eutectic morphology gradually changed from lamellar to partially divorced. The reduction in aluminium content was caused by the growth of an Al-Fe phase ahead of the Mg-Al growth front. Most of the growth of the Al-Fe phase occurred during the remelting period before directional solidification. The thickness of the Al-Fe phase increased with increased temperature and time of contact with the molten Mg-Al alloy. (C) 2003 Maney Publishing.

Preparation, characterization and dielectric properties of temperature stable SrTiO3/PEEK composites for microwave substrate applications

Poly(ether ether ketone) (PEEK) is a potential candidate for electronic applications due to its low permittivity, low loss, high melting point, better chemical resistance, excellent insulating properties and easy processibility. Present paper discusses the preparation and characterization of SrTiO3 filled PEEK composite for microwave substrate applications. The dielectric constant, dielectric loss and temperature variation of dielectric constant of the composites have been studied up to 1 MHz using an Impedance Analyzer. Different theoretical approaches have been employed to predict the effective permittivity of composite systems and the results are compared with that of the experimental data. The crystallinity of the bulk composite is studied by X-ray diffraction studies. Scanning electron microscopic technique has been employed to study the dispersion of the particulate filler in PEEK matrix. Vickers hardness of pure and filled PEEK composite has been measured using Microhardness Tester. The effect of particle size on the dielectric as well as mechanical properties of SrTiO3/PEEK composite system is also studied by incorporating micronsize and nanosize fillers. Present study shows that a temperature stable composite can be realized by judiciously selecting appropriate filler concentration in the PEEK matrix.

Room temperature fast-ion conduction in imidazolium halide salts

Fast-ion conduction has been observed in the iodide and bromide salts of 1-methyl-3-ethylimidazolium at ambient temperatures. The melting point of these two compounds is above 350 K and even at 273 K the ionic conductivity in the solid-state is greater than 10⁻³S cm⁻¹. Cation diffusion coefficients have been measured using fringe field gradient and/or pulse field gradient ¹H NMR techniques, which indicated cation diffusion coefficients of the order of 10⁻¹⁰ m² s⁻¹ in the solid-state. Remarkably, these values are up to an order of magnitude higher than the cation diffusion coefficient in the supercooled liquid at 293 K. The activation energy for diffusion in the solid-state is extremely small, as is typical of solid-state fast-ion conductors and indicates a change in transport mechanism from the melt to the crystal. The inability to detect an ¹²⁷I signal together with the modelling of the conductivity using the Nernst–Einstein equation suggests that the solid-state conduction is primarily due to cation diffusion. The solid-state fast-ion conduction is most likely related to vacancy diffusion along the cation layers in the crystal. The temperature dependence of the NMR signal intensity indicates that the number of mobile species is increasing with increasing temperature with an activation energy of approximately 20–30 kJ mol⁻¹.

Synthesis and properties of ambient temperature molten salts based on the quaternary ammonium ion

The synthesis of 16 tetraalkyl ammonium bis(trifluoromethane sulfonyl) imide salts, (C_nH_2n+1)₄ +N -N (SO₂CF₃)₂ (n = 1, 2, 3, 4),  (C₂H₅)₂(i-C₃H₇)₂ +N -N(SO₂CF₃)₂, (C₂H₅)(CH₃)(i-C₃H₇)₂+N-N(SO₂CF₃)₂, (n-C₇H₁₅)(C₂H₅)i-C₃H₇)₂+N-N(SO₂CF₃)₂ and (C_nH_2n+1)(C_mH_2m+1)₃+N-N(SO₂CF₃)₂ (n = 6,7,8; m = 1, 2, 4) are reported in this paper. Trends in properties of these salts are discussed. The symmetrical tetraalkyl ammonium salts with the bis(trifluoromethyl sulfonyl) imide anion exhibited a lower melting point than that of corresponding ammonium halides. The salts with low symmetry ammonium cations were found to be of generally lower melting point, and many were stable liquids at room temperature. Several of these did not crystallize during cooling below room temperature and exhibited glass transition temperatures in the region of −60 °C∼−80 °C. A comparison of properties between the ammonium imide salts and corresponding trifluoromethane sulfonates is also presented.

Decomposition properties of PVA/graphene composites during melting-crystallization

Abstract The thermal decomposition of PVA and PVA composites during the melting-crystallization process is still unclear due to indistinct changes in chemical compositions. Using graphene as a model, the decomposition properties of PVA and PVA-graphene composites were systematically analyzed under multiple melting-crystallization cycles. And a series of isothermal decomposition experiments around the melting-crystallization temperature were carried out to simulate the corresponding decomposition kinetics. Based on multiple cycle melting-crystallization, the weight loss of PVA and PVA/graphene composites was successfully quantified. Further morphology investigation and chemical structure analysis indicated that the decomposition was non-uniformly distributed, rendering the possibility of crystallization for PVA and PVA/graphene composites after multiple heating-cooling cycles. In addition, isothermal decomposition analysis based on reduced time plot approach and model-free iso-conversional method indicated that Avrami-Eroffev model could well match the decomposition process of the neat PVA and PG-0.3 composite, while the Avrami-Eroffev and first order models could precisely forecast the decomposition of PG-0.9 composite. Both analyses during multiple cycle melting-crystallization and isothermal decomposition demonstrated that graphene served as decomposition accelerator in the whole thermal decomposition process, and particularly the decomposition of neat PVA and PVA/graphene composites was highly related to the band area ratios of C-H and O-H vibrations in Fourier transform infrared (FTIR) spectrum.

A survey on mechanisms and critical parameters on solidification of selective laser melting during fabrication of Ti-6Al-4V prosthetic acetabular cup

Additive Manufacturing (AM) includes a range of approaches that correlate with computer aided design (CAD) and manufacturing by fabrication via precise layers and is a promising method for the production of medical tools. In this study, different aspects and mechanisms of solidification for curved surfaces based on equilibrium at curved interfaces, Monge patch, interfacial and Gibbs energy will be discussed. Also, the effect of capillarity, geometry, substrate temperature, cooling rate and scanning parameters in the solidification of a prosthetic acetabular cup (PAC) using selective laser melting (SLM) is analysed. The contributions of this work are analysing solidification and effective factors in this process to produce parts with a higher quality and mechanical properties such as strength, strain, porosity, relative density and hardness. Results indicate that due to the surface to volume (S/V) ratio, and the increasing effect of the radius on Monge patch, thermal stresses and surface forces are more prevalent on outer surfaces. Moreover, solidification and mechanical properties are related to capillarity, geometry, substrate temperature, cooling rate, scanning power and speed. The results also indicate the interaction of solute diffusion and heat transfer with interatomic forces in large S/V ratio and at small scales tend to improve solidification.